FR2536392A2 - New cyclopropanecarboxylic acid derivatives, process for their preparation and their application to the fight against parasites. - Google Patents

Abstract

The addition is intended to illustrate, by using new examples, the compounds of general formula (I) of the main patent, in which A denotes the residue of an alcohol radical, R denotes an alkyl radical substituted by one or more functional groups or a heterocyclic radical optionally substituted by one or more functional groups or an aryl radical optionally substituted by one or more functional groups. Another subject of the addition is individual processes for the preparation of some of the compounds of the addition. Another subject of the addition is the application of the compounds of the addition to the fight against parasites and the pesticidal compositions containing at least one of the compounds of the addition as active substance.

Description

dans laquelle A représente - soit un radical alcoyle renfermant de 1 à 18 atomes de carbone, - soit un radical benzyle éventuellement substitué par un ou plusieurs radicaux choisis dans le groupe constitué par les radicaux alcoyles comportant de 1 à 4 atomes de carbone, les radicaux alcényles comportant de 2 à 6 atomes de carbone, les radicaux alcényloxy comportant de 2 à 6 atomes de carbone, les radicaux alcadiényles comportant de 4 à 8 atomes de carbone, le radical méthylène dioxyle, le radical benzyle et les atomes d'halogène.In its main patent application filed in France on July 2, 1980 under the number 8014722, entitled "New derivatives of cyclopropane carboxylic acid, their preparation process and their application to the fight against pests and published under the number 2.486.073 , the applicant company has described and claimed, in all possible isomeric forms, isolated or in a mixture, the compounds of formula (I)

in which A represents - either an alkyl radical containing from 1 to 18 carbon atoms, - or a benzyl radical optionally substituted with one or more radicals chosen from the group consisting of alkyl radicals containing from 1 to 4 carbon atoms, the radicals alkenyls containing from 2 to 6 carbon atoms, alkenyloxy radicals containing from 2 to 6 carbon atoms, alkadienyl radicals containing from 4 to 8 carbon atoms, methylene dioxyl radical, benzyl radical and halogen atoms.

dans lequel le substituant R1 représente un atome d'hydrogène ou un radical méthyle et le substituant R2 un aryle monocyclique ou un groupement -CH2-C=CH et notamment le groupement 5-benzyl 3-furyl méthyle, -soit un groupement

dans lequel a représente un atome d'hydrogène ou un radical méthyle, R3 représente un radical organique aliphatique comportant de 2 à 6 atomes de carbone et une ou plusieurs insaturations carbone-carbone et notamment le radical -CH2-CH=CH2, -CH2-CH=CH-CH3, -CH2-CH=CH-CH=CH2, -CH2- CH CH-CH2- CH3 - soit un groupement

dans lequel a représente un atome d'hydrogène ou un radical méthyle, R3 conserve la même signification que précédemment,
R'1 et R'2 identiques ou différents, représentent un atome d'hydrogène, un atome d'halogène, un radical alcoyle renfermant de 1 à 6 atomes de carbone, un radical aryle comportant de 6 à 10 atomes de carbone, un groupement alcoyloxycarbonyle comportant de 2 à 5 atomes de carbone, ou un groupement cyano, - soit un groupement ::

dans lequel B représente un atome d'oxygène, un groupement

ou -CH2- et R4 représente un atome d'hydrogène, un radical -CN, un radical méthyle, un radical -CONH2, ou un radical -CSNH2 ou un radical -C#CH et R5 représente un atome de chlore ou un radical méthyle et n représente un nombre égal à 0, 1 ou 2, et notamment le groupement 3-phénoxy benzyo lique, a-cyano 3-phénoxy benzylique ou a-éthynyl 3-phénoxy benzylique, - soit un groupement

- soit un groupement::

- soit un groupement

dans lequel les substituants R6, R, R8, Rg représentent de l'hydrogène, un atome de chlore, ou un radical méthyle et dans lequel le symbole S/I indique un cycle aromatique ou un cycle analogue dihydro ou tétrahydro, - soit un groupement

et R représente un radical alcoyle renfermant de 1 à 18 atomes de carbone substitué par un ou plusieurs groupements fonctionnels identiques ou différents, ou un groupement aryle renfermant de 6 à 14 atomes de carbone éventuellement substitué par un bu plusieurs groupements fonctionnels identiques ou différents, ou un radical hétérocyclique éventuellement substitué par un ou plusieurs groupements fonctionnels identiques ou différents, composés dans lesquels la double liaison a la géométrie Z ou E, ainsi que les mélanges de ces isomères.- a grouping:

in which the substituent R 1 represents a hydrogen atom or a methyl radical and the substituent R 2 is a monocyclic aryl or a group -CH 2 -C = CH and in particular the 5-benzyl 3-furyl methyl group, or a grouping

in which a represents a hydrogen atom or a methyl radical, R3 represents an aliphatic organic radical containing from 2 to 6 carbon atoms and one or more carbon-carbon unsaturations and in particular the radical -CH2-CH = CH2, -CH2- CH = CH-CH 3, -CH 2 -CH = CH-CH = CH 2, -CH 2 -CH CH-CH 2 -CH 3 - a group

in which a represents a hydrogen atom or a methyl radical, R3 retains the same meaning as above,
R'1 and R'2, which may be identical or different, represent a hydrogen atom, a halogen atom, an alkyl radical containing from 1 to 6 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms, a grouping alkyloxycarbonyl having from 2 to 5 carbon atoms, or a cyano group, - a grouping ::

in which B represents an oxygen atom, a group

or -CH2- and R4 represents a hydrogen atom, a -CN radical, a methyl radical, a -CONH2 radical, or a -CSNH2 radical or a -C # CH radical and R5 represents a chlorine atom or a methyl radical; and n represents a number equal to 0, 1 or 2, and in particular the 3-phenoxy benzyl group, a-cyano 3-phenoxy benzyl or a-ethynyl 3-phenoxy benzyl group, or a grouping

- a grouping ::

- or a group

wherein the substituents R6, R, R8, R6 are hydrogen, chlorine, or methyl, and wherein the symbol S / I indicates an aromatic ring or a similar dihydro or tetrahydro ring;

and R represents an alkyl radical containing from 1 to 18 carbon atoms substituted with one or more identical or different functional groups, or an aryl group containing from 6 to 14 carbon atoms optionally substituted with one or more identical or different functional groups, or a heterocyclic radical optionally substituted with one or more identical or different functional groups, compounds in which the double bond has the Z or E geometry, as well as the mixtures of these isomers.

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

In the main patent, the Applicant Company has also described and claimed the application of the compounds of formula (I) to the control of plant pests, premises, and warm-blooded animals as well as pesticidal compositions containing at least one compound of formula (I) optionally in combination with other compounds;
The present certificate of addition is now intended to illustrate by new examples the general formula (I) of the main patent.

The certificate of addition is more specifically
the compounds corresponding to formula (I) as defined in claim 1 of the main patent whose names follow
- (S) cyano (3-phenoxyphenyl) methyl 1R, cis 2,2-dimethyl-3-oxo-3- (2,2-dichloro-1-cyano vinyloxy) (Z) 7-propenyl / cyclopropane carboxylate
1R, cis 2,2-dimethyl-3-oxo-3 (RS 1,1,1-trichloropropyl-2-oxy) (Z) 1-propenyl / cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) methyl
IR, cis 2,2-dimethyl-3-tetrahydropyran-2-yloxy-3-oxo (Z) 1-propenyl / cyclopropane carboxylate of cyano (3-phenoxyphenyl) methyl
IR, cis 2,2-dimethyl-3-tetrahydrofuran-2-yl-oxy-3-oxo (Z) 1-propenyl / cyclopropane carboxylate cyano (3 phenoxy phenyl) methyl
1R, cis 2,2-dimethyl 3/3-oxo 3 ((S) 1,1,1-trifluoropropyl-2-oxy) (Z) 1-propenyl / cyclopropane carboxylate (s) cyano (3-) phenoxy phenyl) methyl
IR, cis-2,2-dimethyl-3-oxo (R) 1,1,1-trifluoropropyl-2-oxy) (Z) 1-propenyl / cyclopropane carboxylate (S) cyano (3-phenoxy) phenyl) methyl
IR, cis 2,2-dimethyl-3-oxo-3-bromomethoxy (Z) -propenyl / cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) methyl
- (S) cyano (3-phenoxyphenyl) methyl 1R, cis-2,2-dimethyl-3-oxo-3-bromomethoxy (E) 1propenyl / cyclopropane carboxylate
IR, cis-2,2-dimethyl-3-oxo 3- (2,2,2-trifluoro (Rs) 1-ethoxy) ethoxy (Z) 1-propenyl / cyclopropane carboxylate from (S) cyano (3-) phenoxy phenyl) methyl
IR, cis-2,2-dimethyl-3-oxo-3-fluoromethoxy (Z) 1propenyl / cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) methyl
- (S) cyano (3-phenoxyphenyl) methyl 1R, cis 2,2-dimethyl-3-oxo-3-chloromethoxy (Z) 1propenyl / cyclopropane carboxylate
Benzyl 1R, cis 2,2-dimethyl-3-oxo-3- (2-fluoroethoxy) (Z) 1propenyl / cyclopropane carboxylate
1R, 2,2-dimethyl-3/3-oxo-3 (2,2-difluoroethoxy)
(Z) Benzyl 1-propenyl / cyclopropane carboxylate
1R2 cis 2,2-dimethyl-3-oxo-3 (2,2,2-trifluoroetho)
benzyl xy) (Z) 1-propenyl / cyclopropane carboxylate
1R, cis 2,2-dimethyl-3-oxo-3 (1,1,1-3,3,3-hexa)
fluoroisopropoxy) (Z) 1-propenyl / cyclopropane carboxylate
(RS) 1 (6-phenoxy-2-pyridyl) ethyl
1R, cis 2,2-dimethyl-3/3-oxo 3 (RS-1,1,1-trifluoro)
propenyl 2-oxy) (Z) 1-propenyl / cyclopropane carboxylate
(S) cyano (3-phenoxy-4-fluorophenyl) methyl.

dans laquelle représente un nombre égal à 1 on 2 et A conserve les significations précitées, caractérisé l'on fait réagir un acide de formule générale (IV) :

en présence d'ion H+ sur un composé de formule (VI) ::

dans laquelle n conserve la signification précitée, ainsi qu'un procédé de préparation-des composés.de formule (I) répondant à la formule générale (IB)

dans laquelle X représente un atome de fluor, de chlore ou de brome et A conserve les significations précitées, çaracté- risé en ce que l'on fait réagir un acide de formule (iv)

- soit avec le bromure de phosphore PBr3 et du paraformaldéhyde pour obtenir le composé de formule

- soit avec le chlorure de thionyle et du paraformaldehyde pour obtenir le compose de forme::

que l'on traite éventuellement avec le borofluorure d'argent de formule BF4Ag, pour obtenir le composé de formule

The products of the addition may be prepared by the
process of the main patent. Some of them can
advantageously be prepared by other methods. It is
as well as the addition relates to a preparation process
compounds of formula (I) corresponding to the general formula

in which represents a number equal to 1 to 2 and A preserves the aforementioned meanings, characterized by reacting an acid of general formula (IV):

in the presence of H + ion on a compound of formula (VI) ::

in which n has the abovementioned meaning, as well as a process for the preparation of the compounds of formula (I) corresponding to the general formula (IB)

in which X represents a fluorine, chlorine or bromine atom and A has the abovementioned meanings, characterized in that an acid of formula (iv) is reacted;

or with phosphorus bromide PBr3 and paraformaldehyde to obtain the compound of formula

either with thionyl chloride and paraformaldehyde to obtain the compound of form ::

optionally treated with silver borofluoride of formula BF4Ag, to obtain the compound of formula

The products used at the start of the process of the invention are products known in particular from the European patent application 0048186.Some of the starting products to know
- (S) cyano (3-phenoxy-4-fluoro-phenyl) methyl 1R cis 2,2-dimethyl-3-oxo-3-hydroxy (Z) 1-propenyl / cyclopropane carboxylate
Benzyl cis-2,2-dimethyl-3-oxo-3-terbutoxy (Z) 1propenyl cyclopropane carboxylate
Benzyl 1R cis 2,2-dimethyl-3/3-oxo-3-hydroxy (Z) 1propenyl / cyclopropane carboxylate
1- (RS) -2- (6-phenoxy-2-pyridyl) ethyl 1R cis 2,2-dimethyl-3-oxo-3-hydroxy (Z) -propionyl / cyclopropane carboxylate are new products and are in themselves same object of the present invention.

 The invention more particularly relates to these products as intermediates necessary for the implementation of the method of the invention.

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 main patent compounds.

 The addition therefore also relates to the application of the compounds of formula (I) 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 addition can also be used to fight shows insects in the premises, to fight including flies, mosquitoes and cockroaches.

 The products of formula (I) of the addition are also photo stable and are not toxic to mammals.

 All of these properties make products of formula (I) from the addition of 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) 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 compounds of the invention. addition of formula (I).

 The subject of the addition is in particular insecticidal compositions containing as active principle at least one of the compounds of the addition of formula (I).

The compositions of the addition are prepared by
transferred from the agrochemical industry. They can
may be added together with one or more
pesticide agents. These compositions can be presented under
form of powders, granules, suspensions, emulsions, solutions,
solutions for aerosols, fuel belts, .appts or other
preparations conventionally used for the use of this
kind of compounds.

In addition to the active ingredient, these compositions contain, in general, a carrier and / or a surfactant, not
ionic, ensuring, in addition, a uniform dispersion of
constitutive constituents of the mixture. The vehicle used can
be a liquid, such as water, alcohol, hydrocarbons
or other organic solvents, mineral oil, animal
or vegetable, a powder such as talc, clays,
silicates, kieselguhr or a combustible solid,
The insecticidal compositions according to the additions
are preferably from 0.005% to 10% by weight of material
active.

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 addition compositions can then be
advantageously constituted, for the non-active part, of a
coil - fuel, or a substrate
fibrous incombustible. In the latter case, the fumigant ob
held after incorporation of the active ingredient is placed on
a heating device.

In the case where an insecticide coil is used, the
inert support may be, for example, composed of
pyrethrum, Tabu powder (or Machilus leaf powder
Thumbergii), 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,
from 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 5% by weight.

 The compositions according to the addition for use in the premises can also be obtained by preparing a sprayable oil based on 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 can be
added together with one or more other pesticides.

For the acaricidal use, wettable powders are preferably used, for foliar spraying, containing
from 1 to 80 No (or foliar spray liquids with
holding 1 to 500 gel of active ingredient). We can also
foliar powders containing
0.05 to 3% of 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 acaricidal and nematicidal compounds according to the addition
are preferably used in doses of between 1 and
and 100 g of active ingredient per hectare.

The addition therefore also relates to the aca compositions
containing at least one of the active ingredients
compounds of the formula (I) addition as well as
nematicides containing as active principle at least
one of the compounds of the edition of formula (I).

The addition also relates to acari compositions
containing as active ingredient the good at least
from the addition of formula (I), characterized in that
are used in the fight against parasites of warm-blooded animals, especially against ticks and scabies.

 In the case of controlling animal parasitic mites, the products of the addition of formula (I) may be incorporated in 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 tortellol meal of animal origin, 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 a principle
active at least one of the compounds of the addition of formula (I).

The purpose of the addition, therefore, is also that of talented associations
of insecticidal activity, acaricide
or nematicide, characterized in that they contain as active ingredient, on the one hand at least one of the compounds of
the addition of general formula (I) and on the other hand, at least one of the pyrethroid esters selected from the group consti
killed by esters of allethrolones, 3,4,5,6-tetrahydric alcohol
Methyl drophthalimide, 5-benzyl alcohol 3-furyl methyli
3-phenoxy benzyl alcohol and 3-phenoxy benzyl alkenyl alcohols, chrysanthemic acids,
5-benzyl 3-furyl methyl alcohol of 2,2 acids
dimethyl 3- (2-oxo-3-tetrahydrothiopenylidene methyl cyclo)
propane-1-carboxylic acid, by 3-phenoxy alcohol esters
benzyl alcohol and 3-phenoxy benzyl alcohols
2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1 acids
carboxylic acids, by the esters of al-cyano 3-phenoxy benz alcohols
zylics of 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopro acids
pane-1-carboxylic acid, by the esters of alcohol 3-phenoxy ben
2-parachlorophenyl 2-isopropyl acetic acid,
esters of allethrolones, 3,4,5,6-tetrahydro-
methyl phthalimido, 5-benzyl 3-furyl methyl alcohol,
benzyl 3-phenoxy dialcohol and 3-phenoxy-cyano alcohols
benzyl acids 2,2-dimethyl-3- (1,2-2,2-tetrahaloethyl)
cyclopropane-1-carboxylic compounds, in which "halo" represents
a fluorine, chlorine or bromine atom, it being understood that
the acidic mullas and alcohols of the above pyrethrinoid esters can exist in all their possible stereoisomeric forms.

The addition also relates to compositions containing at least one of the compounds of the addition of formula (I)
and in addition, a pyrethrinoid synergist.

 The compositions of the addition may be administered externally, by spraying, by shampooing, bathing or painting.

 They can also be administered by brushing the backbone according to the so-called "for-on" method. They can also be administered by the digestive tract.

 The following examples illustrate the addition without limiting it.

Example 1: 1R, cis 2,2-dimethyl-3-oxo-3- (2,2-dichloro-1-cyano vinyloxy (z) -1-propenyl / cyclopropane carboxylate (S) cyano (3-phenoxy-Dhenyl) methyl.

 In 16 cm3 of methylene chloride, 3.36 g of (S) cyano (3-phenoxyphenyl) -R, cis-2,2-dimethyl-3-oxo-3-hydroxy (Z) -1-propenyl / cyclopropane carboxylate are introduced. ) methyl (prepared in European Application No. 0038271) and 1.7 g of chloral cyanohydrin. It is cooled to OOC, 140 mg of dimethylaminopyridine and then 1.76 g of dicyclohexylcarbodiimide are added and the mixture is stirred for 2 hours 30 minutes at 200 ° C. It is concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica eluting with a mixture of cyclohexane and ethyl acetate (85/15), then chromatographed under pressure to obtain 1.65 g of desired product.

 = = + 400 (c = 0.3% chloroform).

Example 2: 1R, cis 2,2-dimethyl-3-oxo 3- (Rs, 1,1,1-trichloropropyl-2-oxy) (z) -1-propenyl / cyclopropane carboxylate from (S) cyano (3) phenoxy phenyl) methyl.

 3.52 g of 1R, cis-2,2-dimethyl-3-oxo-3-chloro (z) -1-propenyl / cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) methyl are dissolved in 15 cm3 of chloride. of methylene, introduced 5.6 g of trichloroisopropanol, stirred for 19 hours at 20 ° C., poured the reaction mixture over an ice-cold solution of monosodium phosphate, extracted with methylene chloride, the organic phase washed with water and concentrated to dryness with distillation under reduced pressure, chromatography the residue on silica eluting with a mixture of cyclohexane and ethyl acetate (85/15) and obtains 2.85 g of the desired product.

Mp = 780C, D = +500 (c = 1% chloro-oroform).

Preparation: 1 R, cis 2,2-dimethyl-3-chloro-3-oxo (Z) -1-propenyl / cyclopropane carboxylate (S) -yano-o (3-phenoxy phenyl) methyl.

 7.5 g of 1M, cis-2,2-dimethyl-3-hydroxy-3-oxo (Z) -1-propenyl cyclopropane carboxylate (S) cyano (3-phenoxy) are introduced into 7.5 cm 3 of methylene chloride. phenyl) methyl, add a solution of 0.25 cm3 of 1-chloro NN2-trimethylpropenylamine in 7.5 cm3 of methylene chloride, 1.5 cm3 of tert-butanol, stir for 48 hours at 20 ° C, extracted with methylene chloride, washed with water, concentrated to dryness by distillation under reduced pressure, chromatography the residue on silica eluting with a mixture of hexane and ether (8/2) and obtains 0.43 g of desired product .

F = 860C.

Example 3: 1R, cis 3- [3- (tetrahydropyran-2-yloxy) 3-oxo (Z) 1propenyl] -2,2-dimethyl cyclopropane carboxylate (cyano) 3-phenoxyphenyl) methyl.

 10 g of methylene chloride (1.5 g) of 1R, cis 3/3-oxo-3-hydroxy (Z) -1-propenyl / 2,2-dimethyl cyclopropane carboxylate (3-phenoxy phenyl) methyl (solvated with an acetic acid molecule) and 4.5 cm 3 of dihydropyran, stirred at + 150 ° C., added a drop of methanolic N solution of hydrochloric acid, stirred for 30 minutes at room temperature, added calcium carbonate, filter, concentrated to dryness by distillation under reduced pressure, chromatography the residue on silica eluting with hexane ether (8/2) and obtained 1.07 g of desired product.

 = = +470 (c = 0.5% benzene).

Example 4: 1R, cis 3- [3- (tetrahydrofuran-2-yloxy) -3-oxo (Z) -propenyl] -2,2-dimethyl cyclopropane carboxylate of cyano (3-phenoxyphenyl) methyl.

 In a similar manner to that of Example 3, using 4,5-dihydrofuran, the desired product is obtained.

 / δ = + 42.5 (c = 1% benzene).

Example 5: 1R, cis 2,2-dimethyl-3-oxo 3 (R or S) 1,1,1-trifluoropropyl-2-oxy) (Z) 1-propenyl / cyclopropane carboxy (S) cyano ( 3-phenoxyphenyl) methyl (isomer A) and 1R, cis 2,2-dimethyl-3-oxo-3 (S or R) 1,1,1-trifluoropropyl-2-oxy) (z) 1 propenyl / cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) methyl (isomer B).

 In a manner analogous to that of Example 1, after chromatography on silica eluting with cyclohexane-ethyl acetate 9/1), the isomers A and B of the desired product are obtained.

isomer A
Mp = 740C / α / D = + 340 (c = 0.6% chloroform).

Isomer B
F <400C / </ D = +440 (c = 0.5% chloroform).

Example 6: 1 R, cis 3- (3-oxo-3-bromomethoxy (Z) and (E) -1-propenyl) -2,2-dimethyl cyclopropane carboxylate (S) cyano 1- (3-phenoxyphenyl) methyl.

a) Preparation of the acid bromide
In 18 cm3 of toluene, 5.4 g of 1R, cis 3j (Z) 3-oxo-3-hydroxy-1-propenyl / 2,2-dimethyl cyclopropane carboxy are introduced.
(S) cyano (3-phenoxyphenyl) methylate, introduced at -100C,
0.1 cm3 of pyridine, 1.8 cm3 of phosphorus tribromide, stirred for 16 hours at +50 ° C., poured the reaction mixture rapidly into ice water, stirred, decanted the organic phase,
concentrated to dryness by distillation under reduced pressure and ob
holds 4.62 g of acid bromide.

b) Condensation
3.7 g of acid bromide obtained in paragraph a) are mixed,
330 mg of formaldehyde, 100 mg of zinc bromide, bring the reaction mixture to + 500C, keep it there for one hour,
Cool, chromatograph the crude product on silica eluting
with a mixture of cyclohexane and ethyl acetate (8/2)
and obtains 300 mg of ester (Z) and 1 g of ester (E).

isomer (z)
NMR spectrum (CDCl3)
Peaks at 1.27-1.31 ppm, H methylgeminates, peaks at 1.99-2.14 ppm, H at cyclopropyl position 1, peaks at 3.2-3.5 ppm, H at position 3 cyclopropyl peaks at 5.8-5.9 t 5.51 - 6.01 ppm, ii BrCH20pics at 5.9 - 6.1 ppm H ethylenic at 2 ', peak at 6.4 ppm carried by the same carbon than CN, peaks at 6.6 - 6.95 ppm, 1 'ethylenic H, peaks at 6.95 - 7.6 ppm, H aromatic rings.

Isomer (E) / alpha / D = = -18.50 (c = 1.2% chloroform)
Spectrum of RIN (CDCl3)
Peaks at 1.26 - 1.3 ppm, H methyl-geminates, peaks at 1.92-2.17 ppm, H at positions 1 and 3 of cyclopropyl, peak at 5.9 ppm, H of BrCH20pics at 5.9 - 6.2 ppm, ethylenic H 2 ', peak at 6.5 ppm, H borne by the same carbon as the CN group, peaks 7.0 - 7.7 ppm, ethylenic H 1', peaks at 7, 0 - 7.7 ppm, H aromatic rings.

Example 7: 1 R, cis 2,2-dimethyl-3-oxo-3- (RS) -1,1,1-trifluoropropyl-2-oxy) (Z) -1-propenyl cyclopropane carboxylate (S)
cyano (3-phenoxy-4-fluorophenyl) methyl.

 In 10 cm3 of methylene chloride, 2.05 g of 1R, cis 2,2-dimethyl-3-oxo-3-hydroxy-2-propyloxy (Z) -propenyl / cyclopropane carboxylate (3 g cyano (3 phenoxy 4-fluorophenyl) methyl, 2.14 g of 1,1,1-trifluoropropan-2-ol, introduced into OOC, 50 mg of 4-dimethylamino pyridine, 1.3 g of dicyclohexylcarbodiimide, are stirred for one hour and 30 minutes at room temperature. 200C, filtered, the filtrate concentrated to dryness by distillation under reduced pressure, the residue is added 6 cm3 of a mixture of cyclohexane and ethyl acetate (9/1), triturated filter, the filtrate concentrated to dryness by distillation under reduced pressure, the residue chromatographed on silica eluting with a mixture of cyclohexane and ethyl acetate (9/1) and obtained 1.8 g of desired product.

Mp = 880C / 1 / D = +450 (c = 0.5% chloroform).

Preparation of 1R, cis 2,2-dimethyl-3-oxo-3-hydroxy-1 (Z) propenyl / cyclopropane carboxylate (S) cyano (3-phenoxy-4-fluorophenyl) methyl.

 Stage a: 1R, cis-2,2-dimethyl-3-oxo-3-butoxy-1 (Z) propenyl / cyclopropane carboxylate (S) cyano (3-phenoxy-4-fluorophenyl) methyl.

 310 g of (S) cyano (3-phenoxy-4-fluorophenyl) methylalcohol and 310 g of 1R, cis 2,2-dimethyl-3-oxo-3-tert-butoxy-1 ( Z) propenyl / cyclopropane carboxylic acid in 1.55 liter of methylene chloride. A solution of 263.5 g of dicyclohexylcarbodiimide and 3.1 g of dimethylaminopyridine in 530 cm3 of methylene chloride is cooled to -5 ° C. and added at -5 ° C. Stir one hour at -5 C and three hours at room temperature. The mixture is filtered off with suction, the filtrate is washed with N hydrochloric acid and then with water, dried and concentrated to dryness under reduced pressure. The residue is taken up in a mixture of 1.185 liters of isopropanol, 80 cm3 of water and 72 cm3 of triethylamine and stirred for 36 hours. It is filtered, washed with isopropanol and gives 518 g of expected product.

 F = 14040C.

 Step b: 1R, cis 2,2-dimethyl-3-oxo-3-hydroxy-1 (Z) propenyl / cyclopropane carboxylate (S) cyano (3-phenoxy-4-fluorophenyl) methyl.

 350 g of the product obtained above and 35 g of para-toluenesulfonic acid in 3.5 liters of toluene are refluxed for 45 minutes. After cooling, washed with water, the reaction mixture, dried, concentrated to dryness in vacuo and 328 g of crude product.

Example 8: 1 R, cis 2,2-dimethyl-3-oxo-3 (-2,2,2-trifluoro) 1 (RS) ethoxy (Z) -1-propenyl / cyclopropane carboxylate (S) cyano (3-) phenoxy phenyl) methyl.

 In a manner analogous to that of Example 7, using (S) cyano (3-phenoxyphenyl) 1 R, cis-2,2-dimethyl-3-oxo-3-hydroxy (z) -1-propenyl / cyclopropane carboxylate ) methyl and 2,2,2-trifluoro-1-ethoxy ethyl alcohol, the desired product is obtained.

= = +37.5 (c = 1% CHCl3)
Example 9: (S) cyano / 3-phenoxyphenyl) methyl (1R, cis) 2,2-dimethyl-3-oxo-3-chloromethoxy (Z) -1-propenyl) cyclopropane carboxylate.

 A solution containing 18.5 g of 1R, cis 3 / (R) 3-oxo-3-hydroxy-1-propenyl 2,2-dimethyl cyclopropane carboxylate (S) cyano / 3-phenoxyphenyl) is stirred at 20 ° -25 ° C. for two hours. methyl, 50 cm3 of methylene chloride and 50 cm3 of thionyl chloride. We bring dry. 1.38 g of paraformaldehyde and 0.15 g of zinc chloride are added. The suspension is brought to 700C for two and a half hours. After treatment, the product obtained is chromatographed silica eluting with hexane-ethyl acetate (8-2). The desired product is obtained.

NMR spectrum CDCl3
Peaks at 1.27 - 3 H of methyl gemini,
Peaks at 5.9 - 6.1)
6.6 - 7
Peak at 5.8 H of C02CH2Cl
Example 10: (S) cyano (3-phenoxyphenyl) methyl (1R, cis) 2,2-dimethyl-3-oxo-3-fluoromethoxy (z) 1-propenyl / cyclopropane carboxylate.

 Cool to 005, a solution containing 6 g of the product of Example 9 and 60 cm3 of ethyl ether. Silver BF4Ag tetrafluoroboride is added. It is stirred for 30 minutes at 0 ° C. and then one hour and thirty at 200 ° C. The reaction mixture is poured into an aqueous solution of sodium bicarbonate. Wash with water and chromatography on silica eluting with benzene.

1.95 g of the desired product are thus obtained.

NMR spectrum CDCl3
Peaks at 1.27 - 1.3 ppm H of the geminal methyls,
Peaks at 6.6 - 6.8 ppm ethylenic H at the 1 'position,
Peaks at 5.9 - 6.1 ppm ethylenic H at the 2 'position,
Peaks at 5.3 to 6.3 ppm H CO2CH2F.

Example 11: 1R, cis 2,2-dimethyl-3β-oxo-3-fluoroethoxy) (Z) 1-propenyl / benzyl cyclopropanecarboxylate.

 In a manner analogous to that of Example 2, using benzyl 1R, cis 2,2-dimethyl-3/3-oxo-3-hydroxy (Z) 1-propenyl / cyclopropane carboxylate and 2-fluoroethyl alcohol. the desired product is obtained.

 / &alpha; / D = +530 (c = 0.5% chloroform).

Preparation of R, cis 2,2-dimethyl-3-oxo-3-hydroxy-1 (Z) propenyl / benzyl cyclopropane carboxylate.

Stage a: 1R, benzyl-e cis 2,2-dimethyl-3β-oxo-3-tertbutoxy 1 (Z) propenyl / cyclopropane carboxylate.

 It is cooled to 1000, 2.6 g of sodium hydride in 100 cm 3 of tetrahydrofuran and 25 g of (lR, cis) 2,2-dimethyl-3-oxo-3-tertbutoxy-1 (Z) propenyl acid are added. / cyclopropane carboxylic acid (prepared in European Application No. 0041021) in 250 cm3 of tetrahydrofuran. Stirred 30 minutes at 15 C, added 35 cm3 of benzyl bromide in 100 cm3 of tetrahydrofuran and heated at 50 C for 48 hours.

The cooled reaction mixture is poured onto a monosodium phosphate aqueous solution and extracted with isopropyl ether, washed with water, dried and concentrated to dryness under reduced pressure. The residue is chromatographed on silica eluting with hexane-isopropyl ether (9/1).

30 g of expected product are obtained
Stage b: 1R, cis 2,2-dimethyl-3β-oxo-3-hydroxy-1 (Z) propenyl / benzoyl cyclopropane carboxylate.

 5 g of the product obtained above are refluxed for one hour in 30 cm3 of toluene and 250 mg of para-toluenesulphonic acid.

After cooling, chromatography on silica eluting with hexane-ethyl acetate (1-1) containing 1 percent of acetic acid. After recrystallization from isopropyl ether, 3.05 g of expected product is obtained.

F = 690C.

Preparation of (R, S) 1- (6-phenoxy-2-pyridyl) ethyl (1 R, cis) 2,2-dimethyl-3-oxo-3-hydroxy-1 (Z) propenyl / cyclopropane carboxylate.

 Step a: (1 R, cis) 2,2-dimethyl-3-oxo-3-butoxy-1 (Z) propenyl / cyclopropane carboxylate (R, S) 1- (6-phenoxy-2-pyridyl) ethyl.

65 g of (1R, cis) 2,2-dimethyl-3-oxo acid are mixed together.
terbutoxy 1 (Z) pTopenyl / cyclopropane carboxylic acid, 650 cc
methylene chloride and 70 g of alcohol (RS) 1- (6-phenoxy)
2-pyridyl) ethyl and cooled to + 50C. We add to 50C
in 25 minutes a solution of 55.7 g of dicyclohexylcarbodiimide
and 2.6 g of dimethylaminopyridine in 450 cm3 of chloride
methylene. After stirring for 4 hours at 200.degree.
precipitated and concentrated to dryness the filtrate. The residue is taken up
by 240 cm3 of ethyl ether. It is drained, concentrated to dryness
filtrate and chromatograph the residue on silica eluting with
a mixture of n-hexane-ethyl acetate (100-4).

 101 g of expected product are obtained.

 = = +640 (c = 1% toluene).

Stage b: (1R, cis) 2,2-dimethyl-3-oxo-3-hydroxy-1 (Z) propene
(R, S) 1- (6-phenoxy-2-pyridyl) nyl / cyclopropane carboxylate
ethyl.

Refluxed 5,649 g of product obtained above and
0.5 g of para-toluenesulfonic acid in 70 cm3 of toluene
until the end of gassing.

It is cooled to OOC, filtered, concentrated to dryness the filtrate
and obtains 4,741 g of expected product.

Example 12: 1R, cis 2,2-dimethyl-3-oxo-3- (2,2-difluoroethoxy)
(Z) 1-propenyl / benzyl cyclopropane carboxylate.

In a similar manner to that of Example 7, using the
1R, cis 2,2-dimethyl-3-oxo-3-hydroxy (Z) -1-propenyl
benzyl cyclopropane carboxylate and difluoroethyl alcohol
lique, we obtain the desired product.

 / / D = + 520 (c = 0.2% chloroform).

Example 13: IR, cis 2,2-dimethyl-3-oxo 3- (2,2,2-trifluoro)
ethoxy) (Z) 1-propenyl / benzyl cyclopentyl carboxylate.

In a manner analogous to that of Example 7, using
1R, cis 2,2-dimethyl-3-oxo-3-hydroxy (Z) -1-propenyl
benzyl cyclopropane carboxylate and trifluoro alcohol
ethyl, the desired product is obtained.

 = = +450 (c = 0.6% chloroform).

Example 14: 1R, cis-2,2-dimethyl-3-oxo-3- (1,1,1-3,3,3-hexafluoroisopropoxy (Z) propenyl / cyclopropane carboxylate of (RS) 1- (6-phenoxy) 2-pyridyl) methyl.

 By following a procedure analogous to that of Example 7, using 1 R, cis 2,2-dimethyl-3-oxo-3-hydroxy (Z) -1-propenyl / cyclopropane carboxylate (R 9 S) 2- (6) phenoxy pyridyl) methyl. The expected product is obtained.

/ </ D = +550 (c = 0.2% chloroform).

Examples of compositions
Example 15: Preparation of a soluble concentrate

A homogeneous mixture of product of Example 9 (isomer A) is carried out ......... 0.25 g - Piperonyl butoxide OO. > 1 g - Tween 80 ........................ 0.25 g - Topanol A ............. .......... 0.1 g - Water ............................. 98.4 g
Example 16: Preparation of an emulsifiable concentrate.

The product of Example 9 (isomer B) is mixed thoroughly with 0.015 g. Piperonyl butoxide 0.5 g. Topanol A .................... , 1 g - Xylene v 95.885 g - Tween 80 ....................... 3.5 g
Example 17: Preparation of an emulsifiable concentrate.

A homogeneous mixture of: - Product of Example 11 ......... 1.5 g - Tween 80 .................... .... 20 g - Topanol A ....................... 0,1 g - Xylene ............ .............. 78.4 g
Example 18: Preparation of a smoke composition.

 Mixed in a homogeneous manner: - Product of Example 8 .......... 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 Addition compounds
A. Study of the slaughter effect on house flies
Test insects are female house flies
4 days old. It is carried out by direct spraying at a concentration of 0.25 g / l in a Kearns and March chamber using as solvent a mixture of acetone (5%) and Isopar L (petroleum solvent) (amount of solvent used 2 ml in one second). 50 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.

COMPOUNDS KT solen min of Example 7 2.89 of Example 8 3.93 of Example 12 2.17
of example 13 4.90
of Example 10 5.30.

B. Study of the lethal effect on house flies
Test insects are female house flies
4 to 5 days old. We operate by topical application of 1
of acetone solution on the dorsal thorax of insects to
the help of Arnold's micro-manipulator. 50 individuals are used per treatment. We carry out the mortality control twenty
four hours after treatment.

The results obtained expressed in LD 50 or dose (in nano
grams per individual needed to kill 50% of insects,
are the following
LD 50 COMPOUNDS IN NG / INSECT
Example 9 (Isomer A) 0.50
Example 9 (Isomer B) 0.54
C. Study of the lethal effect on cockroach
The tests are carried out by contact on glass film,
by pipetting, acetone solutions of
different concentrations on the bottom of a glass Petri dish
whose edges have been previously talcated to avoid
insect leakage. The lethal concentration is determined 50
(CL 50).

The experimental results obtained are summarized in the
next table
CL 50 COMPOUNDS in MG / M2
of example 4 1.77 of example 9 (isomer A) 0.07 of example 9 (isomer B) 0.122
D. Study of the lethal effect on larvae of Spodoptera Littoralis
The tests are performed by topical application of an acetone solution using the Arnold micro-manipulator on the dorsal thoracic larvae. Fifteen larvae are used per dose of product to be tested. The larvae used are fourth instar larvae, i.e., about 10 days old when raised at 240C and 65% relative humidity.

After treatment, the individuals are placed on an artificial nutrient medium (Poitout medium).

 Mortality control is performed 48 hours after treatment.

The experimental results obtained are summarized in the following table
LD 50 COMPOUNDS IN NG / INSECT
Composed of example 9
(isomer A) 9.0
Composed of example 9
(isomer B) 8.46.

E. Study of the lethal effect on Aphis Cracivora
Adults of 7 days are used and 10 Aphis are used per concentration used. A contactinjection method is used. Fisher's spray treatment of a bean leaf which is deposited in a plastic petri dish is carried out on a washer of moistened paper. The treatment is carried out using 2 ml of test product acetone solution (1 ml per sheet face). Insect infestation is performed after drying the leaf. The insects are kept in contact with the leaf for one hour. The insects are placed on untreated leaves and the mortality is checked after 24 hours.
The experimental results obtained are summarized in the following table
LD 50 / NG / INSECTE COMPOUNDS of Example 1 6.6 of Example 35.5 of Example 4 0.80 of Example 9 (A isomer) 6.3 of Example 9 (isomer B) 5.8.

F. 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 spray: 4 ml of solution to be tested, containing the pyrethroid, per plant of a mixture of equal volume of water and acetone. Allow to dry for 12 hours 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 for which 50% mortality is obtained.

The experimental results obtained are summarized in the following table
COMPOUND CL 50 enMG / HL
Composed of example 9
(isomer A). 676 *
Composed of example 9
(isomer B) 501.

G. Conclusion
In the tests used, the compounds of the Addition exhibit a good insecticidal activity and a good acaricidal activity.

Claims (10)

 1) The compounds corresponding to formula (I) as defined in claim 1 of the main patent whose names follow  - (S) cyano (3-phenoxyphenyl) methyl 1R, cis 2,2-dimethyl-3-oxo-3- (2,2-dichloro-1-cyano-vinyloxy) (Z) propenyl / cyclopropane carboxylate;  1R, cis 2,2-dimethyl-3-oxo-3 (RS 1,1,1-trichloropropyl-2-oxy) (Z) 1-propenyl / cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) methyl  cyano (3phenoxyphenyl) methyl 1R, cis 2,2-dimethyl-3-tetrahydropyran-2-yloxy-3oxo (Z) 1-propenyl / cyclopropane carboxylate  IR, cis 2,2-dimethyl-3-tetrahydrofuran-2-yl-oxy-3-oxo (Z) 1-propenyl / cyclopropane carboxylate of cyano (3-phenoxyphenyl) methyl  IR, cis 2,2-dimethyl 3/3-oxo 3 ((S) 1,1,1-trifluoropropyl-2-oxy) (Z) 1-propenyl / cyclopropane carboxylate (S) cyano (3-) phenoxy phenyl) methyl  - 1R, cis 2,2-dimethyl 3/3-oxo 3 ((R) 1,1,1-trifluoropropyl 2-oxy) (Z) 1-propenyl / cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) ) methyl  IR, cis 2,2-dimethyl-3-oxo-3-bromomethoxy (Z) 1propenyl / cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) methyl  - (S) cyano (3-phenoxyphenyl) methyl 1R, cis-2,2-dimethyl-3-oxo-3-bromomethoxy (E) -propenyl / cyclopropane carboxylate  1R, cis-2,2-dimethyl-3-oxo-3- (2,2,2-trifluoro (RS) 1-ethoxy) ethoxy (Z) 1-propenyl / cyclopropane carboxylate (S) cyano (3-) phenoxy phenyl) methyl  - (S) cyano (3-phenoxyphenyl) methyl 1R, cis-2,2-dimethyl-3-oxo-3-fluoromethoxy (Z) -propenyl / cyclopropane carboxylate  cyano (3-phenoxyphenyl) methyl 1R, cis 2,2-dimethyl-3-oxo-3-chloromethoxy (Z) -propenyl / cyclopropane carboxylate  Benzyl 1R, cis 2,2-dimethyl-3/3-oxo 3 (2-fluoroethoxy (Z) 1-propenyl / cyclopropane carboxylate  - IR, cis 2,2-dimethyl-3/3-oxo 3 (2,2-difluoroethoxy) (Z) 1-propenyl / benzyl cyclopropanecarboxylate  Benzyl 1R, cis 2,2-dimethyl-3-oxo-3 (2,2,2-trifluoroethoxy) (Z) I-propenyl / cyclopropane carboxylate  iR, cis 2,2-dimethyl-3-oxo-3 (1,1,1-3,3,3-hexafluoroisopropoxy) (Z) i-propenyl / cyclopropane carboxylate (RS) 1 (6-phenoxy 2 pyridyl) ethyl  IR, cis-2,2-dimethyl-3-oxo-3 (RS-1,1,1-trifluoro-propenyl-2-oxy) (Z) 1-propenyl / cyclopropane carboxylate (S) cyano (3-phenoxy) -fluorophenyl) methyl.  2) Process for the preparation of the compounds of formula (I) corresponding to the general formula (IA)

 in which n represents a number equal to 1 or 2 and A preserves the abovementioned meanings, characterized in that an acid of general formula (IV) is reacted:

 in the presence of H + ion on a compound of formula (VI)

 in which n retains the above-mentioned meaning.  3) Process for preparing compounds of formula - (I) corresponding to general formula (IB)

  in which X represents a fluorine, chlorine or bromine atom and A has the abovementioned meanings, characterized in that an acid of formula (IV) is reacted

 or with phosphorus bromide PBr3 and paraformaldehyde to obtain the compound of formula:

 or with thionyl chloride and paraformaldehyde to obtain the compound of formula

 optionally treated with silver borofluoride of formula BF4Ag, to obtain the compound of formula

 4) Application of the compounds as defined in claim 1 to the control of plant pests, local parasites and parasites of warm-blooded animals.  5) 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 7.  6) The insecticidal compositions containing as active principle at least one of the products defined in the revendica tionl.  7) The acaricide compositions containing as active ingredient at least one of the products defined in claim 1.  8) nematicide compositions containing as active ingredient at least one of the products defined in claim 1.  9) 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.  10) The compositions intended for animal feed containing as active ingredient at least one of the products defined in claim 1.  i1) 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 pyrethrinol esters selected from the group consisting of esters of allethrolones, 3,4,5,6-tetrahydrophthalimido methyl alcohol, 5-benzyl-3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and alcohols. cyano 3-phenoxy benzyl chrysanthemic acids, by the esters of alcohol 5-benzyl 3-furyl methyl 2,2dimethyl 3- (2-oxo-3-tetrahydrothiophenylidene methyl) cyclopropane-1-carboxylic acids, by the esters of alcohol 3- benzyl phenoxy and 3-phenoxy benzyl α-cyano alcohols of 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1 carboxylic acids, by the esters of 3-phenoxy benzyl α-cyano alcohols 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopro pane-1-carboxylic acids, by the esters 3-phenoxy benzyl alcohol, 2-parachlorophenyl 2-isopropyl acetic acid esters, allethrolone esters, 3,4,5,6-tetrahydrophthalimido methyl alcohol, 5-benzyl 3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and 3-phenoxy benzyl α-cyano alcohols of 2,2-dimethyl-3- (1,2,2,2-tetrahaloethyl) cyclopropane-7-carboxylic acids, in which "halo!" represents a fluorine, chlorine or bromine atom, it being understood that the acidic copula and alcohols of the pyrethrinoid esters above may exist in all their possible stereoisomeric forms.  12) The compositions according to any one of claims 5 to 11, characterized in that they contain, in addition, a pyrethrinode synergist.  13) As intermediate products necessary for carrying out the process according to claim 3:  IR cis 2,2-dimethyl-3-oxo-3-hydroxy (Z) -propenyl / cyclopropane carboxylate (S) cyano (3-phenoxy-4-fluoro phenyl) methyl  IR cis 2,2-dimethyl-3/3-oxo-3-terbutoxy (Z) 1-propenyl / benzyl cyclopropanecarboxylate  IR cis 2,2-dimethyl-3/3-oxo-3-hydroxy (Z) -propenyl / benzyl cyclopropane carboxylate;  IR cis 2,2-dimethyl-3-oxo-3-hydroxy (Z) -propenyl / cyclopropane carboxylate (RS) 1- (6-phenoxy-2-pyridyl) ethyl.