FR2570698A1 - ESTERS OF CYCLOPROPANE CARBOXYLIC ACIDS AND DIACETYLENIC ALCOHOLS, PROCESS FOR PREPARING THEM AND THEIR USE IN THE FIGHT AGAINST PESTS - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS THE COMPOUNDS RESPONDING TO GENERAL FORMULA I: (CF DRAWING IN BOPI) IN WHICH R AND R REPRESENT A HYDROGEN ATOM OR AN ALKYL RADICAL. EITHER R REPRESENTS A RADICAL: (CF DRAWING IN BOPI) IN WHICH THE GEOMETRY OF THE DOUBLE LINK IS E OR Z AND IN WHICH R REPRESENTS A HYDROGEN, FLUOR, CHLORINE OR BROMINE ATOM, OR AN ALCOHOL OR ALCOHOL RADICAL , Z REPRESENTS AN ATOM OF OXYGEN OR SULFUR AND R REPRESENTS: -OR A RADICAL ALKYL WHICH IS POSSIBLE SUBSTITUTES; - OR A POSSIBLY SUBSTITUTE ARYLE GROUP; - OR A HETEROCYCLIC RADICAL POSSIBLY SUBSTITUTES AN OXYGEN OR SULFUR ATOM, A SULFOXIDE GROUP OR A SULPHONE GROUP AND, - OR R REPRESENTS AN ALCOHYL RADICAL; -OR R REPRESENTS A RADICAL ARYL OR ARALCOYL; - EITHER R REPRESENTS A RADICAL: (CF DRAWING IN BOPI) IN WHICH HAL REPRESENTS A HALOGEN ATOM. THE COMPOUNDS OF THE INVENTION HAVE INTERESTING PESTICIDE PROPERTIES.

Description

1 2570698

  The invention relates to novel esters derived from cyclopropane carboxylic acids and diacetylenic alcohols, their process

  preparation and their application to pest control.

  The subject of the invention is the compounds corresponding to the general formula I:

H3C.CH3

R3 - / C02CH-CCR1 (I)

  Wherein R1 and R2 are the same or different from each other and represent a hydrogen atom or an alkyl radical having from 1 to 8 carbon atoms, and: R3 represents a radical:

R4 H

  RZOC in which the geometry of the double bond is E or Z and wherein R4 represents a hydrogen atom, or a fluorine, chlorine or bromine atom, or an alkyl or alkoxyl radical containing from 1 to 8 carbon atoms Z represents an oxygen or sulfur atom and R represents: - either a linear, branched or cyclic alkyl radical, saturated or unsaturated, containing from 1 to 18 carbon atoms, optionally substituted with one or more identical functional groups or different, 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 a

  or several functional groups, identical or different.

- or R3 represents a radical:

R5A H

i C = C-

N: C

2 2570698 V

  in which A represents an oxygen or sulfur atom, a sulphoxide group or a sulphone group and, - or else R 5 represents a linear, branched or cyclized alkyl radical, saturated or unsaturated, containing up to 18 carbon atoms, of which the chain may be interrupted by one or more heteroatoms and, or substituted by one or more halogen atoms, - or R5 represents an aryl or aralkyl radical containing

up to 18 carbon atoms.

  or R 3 represents a radical: Hal H C = C-N-C / in which Hal represents a halogen atom, in all the possible stereoisomeric forms as well as all the mixtures of

possible stereoisomers.

  The compounds of formula I can exist in many stereoisomeric forms: they have, in fact, two asymmetric carbons at the 1 and 3 positions of the cyclopropane. They can present

  also other centers or axes of asymmetry in the radical R3.

  When R1 or R2 represents an alkyl radical, it is

  preferably methyl, ethyl, n-propyl or isopropyl.

When R3 represents a radical:

R4 / H

RZOC /

  it is preferably a radical in which R represents one of the values indicated as preferred values of R in the European patent applications 0038271, 0041021, 0048186, 0050534, 0077721 and

0108679.

  When R 4 or R 5 represents an alkyl radical, it is preferably methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl or tert-butyl, optionally interrupted by an oxygen or sulfur atom, and optionally substituted with one or more fluorine, chlorine, bromine atoms, or

still vinyl radical.

  When R4 represents an alkoxyl radical, it is

  preferably the methoxy or ethoxy radical.

  When R5 represents an aryl or aralkyl radical, it is

  preferably phenyl or benzyl.

  When R3 represents a radical: Hal H C = Cs NEC the preferred values of Hal are fluorine, chlorine and bromine. The subject of the invention is especially the compounds of formula I, for which R 1 and R 2 represent a hydrogen atom. Among the preferred compounds of the invention, mention may be made of the compounds in which R 3 represents a radical:

R4 /

R02C /

  in which the geometry of the double bond is E or Z, R and R4 retaining the same meaning as before. Among these compounds, mention may be made of the compounds in which R represents a linear or branched alkyl radical containing from 1 to 8 carbon atoms, for example a methyl, ethyl, isopropyl or terbutyl radical, or the compounds in which R represents a linear or branched alkyl radical. an alkyl radical containing from 1 to 8 carbon atoms substituted with one or more halogen atoms, with one or more fluorine atoms for example; this is how, as a value of R, we can cite the radical

-CH2CF3.

  The subject of the invention is particularly the compounds of formula I, in which R 3 represents a radical

R4 H

  Where R4 represents a hydrogen atom, the geometry of the double bond is Z and the structure of the cyclopropane copula is lRcis. Among the preferred compounds of the invention, mention may also be made of the compounds of formula I in which R 3 represents a radical

R4 _H

R02CJ

4 2570698

  in which R4 represents a fluorine, chlorine or bromine atom, the geometry of the double bond is E and the structure of the copula

cyclopropane is lcis.

  The subject of the invention is particularly the compounds in which R4 represents a fluorine atom. Among the preferred compounds of the invention include compounds whose preparation is given later in the experimental part. The invention also relates to a process for the preparation of the compounds of formula I, characterized in that an acid of formula II is subjected to:

CH3 \ CH3

I

R3 / CO02H

  in which R3 retains its previous meaning, or a functional derivative of this acid, in the action of an alcohol of formula:

C = CR1

I

HO-CH III

  C-CR2 in which R1 and R2 retain their previous meaning, or a functional derivative of this alcohol, to obtain the compound of

corresponding formula I.

  According to a preferred embodiment of the process of the invention, the acid of formula II is esterified with the alcohol of formula III in the presence

  dicyclohexylcarbodiimide and 4-dimethylaminopyridine.

  The products of formula I may also be prepared according to alternative embodiments of the process described above, obvious to those skilled in the art. Thus, when it is desired to prepare compounds of formula I in which R 3 represents a radical:

R4 H

_-- C = C /

R02C

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  that is to say, when it is desired to prepare compounds corresponding to the formula:

R4 H H3C CH3

C = C / C02-CH-C-CR1

  R02C C-CR2 can first be prepared the acid of formula:

R4 H

C = C CO2-CH-CECR1

  Which is esterified according to the usual methods to obtain the corresponding ester corresponding to formula I. The acids of formula II are known products, described for example in European patents 0038271, 0041021, 0048186, 0050534,

  007721, 0108679, as well as in the French patent application 2536389.

  Alcohols of formula III are also known products

  which can be prepared according to the process described by R LESPICAU, Bull.

  Soc. Chim. 6, 947-9 (1939) or the method described by JONES et al.

J. Chem. Soc. (1960), 3483-9.

  The compounds of formula (I) have interesting properties

  which allow their use in the fight against pests.

  This may include, for example, the control of plant pests, parasites of premises and parasites of warm-blooded animals. Thus, the compounds of the invention can be used to control insects, nematodes and mites.

  parasites of plants and animals.

  The subject of the invention is thus the application of the compounds of formula I to the fight against plant pests and diseases.

parasites of the premises.

  The products of formula (I) can 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 between 10 9 and

  300 g of active ingredient per hectare.

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  The products of formula (I) may also be used to control insects in the premises, in particular to fight against flies, mosquitoes and cockroaches, as well as to fight against insect pests of animals, for example lice, in particular in cattle, sheep and poultry. The products of formula (I) can also be used to

  fight against mites and plant parasitic nematodes.

  The compounds 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.

  The subject of the invention is also compositions intended for combating plant pests, premises parasites and parasites of warm-blooded animals, characterized in that they contain as active ingredient at least one of the products defined above. The invention particularly relates to the insecticidal compositions containing as active ingredient at least one of the products defined above. The subject of the invention is also the acaricide compositions containing as active principle at least one of the products defined above as well as the nematicidal compositions containing as

  active ingredient at least one of the products defined above.

  The invention also relates to 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 scabies.

  Among the preferred pesticidal compositions of the invention, mention may be made especially of compositions containing the compounds

described in the examples.

  These compositions are prepared according to the usual methods of

  the agrochemical industry. They may be added together

  one or more other pesticide agents.

  These compositions may be in the form of powders, granules, suspensions, emulsions, solutions, aerosol solutions, combustible strips, baits or other preparations conventionally used

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  for the use of this kind of compounds.

  In addition to the active ingredient, these compositions generally contain a vehicle and / or a nonionic surfactant which

  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, a mineral oil, animal or vegetable oil, a powder such as talc, clays,

  silicates, kieselguhr or a combustible solid.

  The insecticidal compositions according to the invention contain

  preferably from 0.005% to 10% by weight of active material.

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

fumigant compositions.

  The compositions according to the invention can then be advantageously constituted, for the non-active part, a combustible coil, or a non-combustible fibrous substrate. In the latter case, the fumigant obtained after incorporation of the material

  active is placed on a heating device.

  In the case where an insecticide 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 (as

  sawdust) starch and coconut shell powder.

  The dose of active ingredient can then be, for example, 0.03

at 1% by weight.

  In the case where a noncombustible fibrous support is used, the dose of active ingredient can then be, for example, from 0.03 to

% in weight.

  The compositions according to the invention 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 being

then subjected to combustion.

  The concentration of the active ingredient incorporated in the oil is,

  preferably from 0.03 to 25% by weight.

  The acaricide and nematicide compositions may be in particular in the form of powders, granules, suspensions, emulsions, solutions. The acaricide and nematicide compositions can be

  optionally added with one or more other pesticidal agents.

  For the acaricidal use, wettable powders, for foliar spraying, containing from 1 to 80% of

8 2570698

  active ingredient or foliar spray liquids containing from 1 to 500 g / l of active ingredient. Leaf dusting powders containing 0.05 to 3% active ingredient may also be used. For nematicide use, liquids are preferably used

  for soil treatment containing from 300 to 500 g / l of active ingredient.

  The acaricidal and nematicidal compounds according to the invention are preferably used at doses of between 1 and 100 g of

active ingredient per hectare.

  When it comes to controlling animal parasitic mites, it is possible to incorporate the products of the invention into food compositions in combination with a nutrient 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, acids

  synthetic amines, mineral salts, vitamins and anti-

  oxidants. The invention therefore also relates to compositions for animal feed containing an active ingredient

  at least one of the products defined above.

  When it comes to combating animal parasitic mites, the compositions of the invention may be administered externally, by spraying, by shampooing, by bathing, or by

  brushing of the backbone according to the "for-on" method.

  The invention 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 compounds of general formula (I) and on the other hand, at least one of 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 o-cyano-3-phenoxy benzyl alcohols of chrysanthemic acids,

  5-benzyl-3-furyl methyl alcohol esters of 2,2-

  dimethyl 3- (2-oxo-3-tetrahydrothiophenylidene methyl) cyclopropane-1

  carboxylic acids, by the 3-phenoxy benzyl alcohol esters and

  o-cyano 3-phenoxy benzyl alcohols of 2,2-dimethyl-3- (2,2-dimethyl)

  dichlorovinyl) cylopropane-1-carboxylic acid esters of alcohols

  -cyano 3-phenoxy benzyl acids 2,2-dimethyl-3- (2,2-

  dibromovinyl) cyclopropane-1-carboxylic acid esters by 3-phenoxy benzyl alcohol esters of 2-parachlorophenyl 2-isopropyl acids

  acetic acid esters of allethrolones of 3,4,5,6-tetrahydro-

  methyl phthalimido, 5-benzyl 3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and o-cyano-3-phenoxy benzyl alcohols of 2,2-dimethyl-3- (1,2-2,2-tetrahaloethyl) cyclopropane-1-carboxylic acid, in which "halo" represents a fluorine, chlorine or bromine atom, it being understood that the acidic moles and alcohols of the above pyrethroid esters may exist in all their

possible stereoisomeric forms.

  To enhance the biological activity of the products of the invention, they can be added to conventional synergists used in such a case such as 1- (2,5,8-trioxadodecyl) -2-propyl 4,5-methylene dioxy benzene ( or piperonyl butoxide) or N- (2-ethylheptyl)

  bicyclo / 2,2-1) -5-heptene 2,3-dicarboximide or piperonyl-bis-2- (2'-n-

  butoxyethoxy) ethylacetal (or tropital).

  The invention therefore also relates to the compositions and associations as defined above, characterized in that

  they contain, in addition, a synergist pyrethrinoids.

  The following examples illustrate the invention without however the

limit.

  EXAMPLE 1 (1R, cis, E) 2,2-dimethyl-3/2-fluoro-3-oxo-3-methoxy-propynyl-cyclopropane carboxylate penta 1,4-diyn-3-yl: 0.7 g of penta 1 are mixed 4-diyn 3-ol, 1.08 g of acid (1R, cis;

  E) 2,2-dimethyl-3-fluoro-3-oxo-3-methoxy-propenyl / cyclopropane-1

  carboxylic acid prepared as indicated in Preparation 4 of the French patent application 2536389, 15 cm3 of methylene chloride, cooled to 0 C and added 50 mg of 4-dimethylamino pyridine, then a solution of 1.03 g of dicyclohexyl carbodiimide in 5 cm 3 of methylene chloride, stirred for 2 hours at 20 ° C., the precipitate formed is filtered off, the filtrate is concentrated to dryness by distillation under reduced pressure and 1.9 g of crude title compound are obtained, which is chromatographed on silica gel. eluting with a mixture of hexane and

  of ethyl acetate (9/1) and gives 1 g of the desired compound.

  // D = +36 + 2.5 (c = 0.4%, chloroform).

  EXAMPLE 2 (1R, cis, E) 2,2-dimethyl-3-fluoro-3-oxo-3-tert-butoxypropenyl / cyclopropane carboxylate penta 1,4-diynyl-3-yl: 2.5 g of penta 1,4-diyn 3-ol, 6.8 g of (1R, cis; E) 2,2-dimethyl-3-fluoro-3-oxo, 3-tert-butoxypropenyl / cyclopropane carboxylic acid prepared as indicated in the preparation French Patent 2536389, 25 cm3 of methylene chloride, introduced 100 mg

2570698

  of dimethylamino pyridine, cooled to 0 ° C and a solution of 5.4 g of dicyclohexyl carbodiimide in 10 cm3 of methylene chloride, stirred for 16 hours at 20 ° C., filtered off the precipitate formed, concentrated the filtrate to dryness by distillation under reduced pressure and obtained 10.3 g of desired crude compound, which is chromatographed on silica eluting with a mixture of hexane and

  of ethyl acetate (95/5) and gives 6.1 g of the desired compound.

  // D = + 57.5 + 1 (c = 2%, chloroform).

  EXAMPLE 3 (1R, cis, Z) 2,2-dimethyl-3-oxo-3-tert-butoxypropenyl / cyclopropane carboxylate penta 1,4-diynyl:

  4.8 g of (1R, cis; Z) 2,2-dimethyl-3-oxo-3-oxo acid are mixed together.

  tert butoxy propenyl / cyclopropane carboxylic acid, 2 g of penta 1,4-diyn 3ol prepared as indicated in European Patent 0041021 preparation 8 cm3 of methylene chloride, introduced 50 mg of dimethylamino pyridine and then cooled to OC and added a solution of 4 0.5 g of dicyclohexyl carbodiimide in 10 cm3 of methylene chloride, stirred for 16 hours at 20 ° C., the precipitate formed is filtered off with suction, the filtrate is concentrated to dryness by distillation under reduced pressure and 7.5 g of the crude title compound are obtained. chromatography on silica eluting with a mixture of hexane and ethyl acetate (9/1)

  and obtained 4.5 g of desired compound F = 91 C.

  /? </ D = + 75 + 1 (c = 1%, chloroform).

  EXAMPLE 4 (1R, cis, E) 2,2-dimethyl-2-fluoro-3-oxo-3-ethoxypropenyl / cyclopropane carboxylate penta 1,4-diynyl-3-yl 3.5 g of acid ( 1R, cis; E) 2,2-dimethyl-2-fluoro-3-oxo-3-ethoxypropenyl / cyclopropane carboxylic acid, as indicated in French Patent 2491060, Example 6, 1.5 g of penta-1,4-diyn-3-ol 25 cm3 of methylene chloride, cooled to 0 ° C. and added 35 mg of dimethylamino pyridine, then a solution of 3 g of dicyclohexyl carbodiimide in 10 cm 3 of methylene chloride, stirred for 3 hours at 20 ° C., the precipitate was filtered off. formed, concentrated the filtrate to dryness by distillation under reduced pressure to obtain 9 g of crude title compound which was chromatographed on silica eluting with a mixture of hexane and ethyl acetate (9/1) and

  2.9 g of desired product.

  / Λ / D = +43.5 + 1.5 (c = 1.2%, chloroform).

  EXAMPLE 5 (1R, cis, Z) 2,2-dimethyl-3-methoxy-3-oxopropenyl / cyclopropane carboxylate penta 1,4-diynyl-3-yl: 3 g of acid (1R, cis; Z) 2,2-dimethyl-3-methoxy-3-oxo-propenyl / cyclopropane carboxylic acid prepared as indicated in the preparation of French Patent 2480748, 1.5 g of penta-1,4-diyn-3-yl, cm 3 of methylene chloride , cooled to 0 ° C., 30 mg of dimethylamino pyridine and then a solution of 3 g of dicyclohexyl carbodiimide in 15 cm 3 of methylene chloride, stirred for 3 hours at 20 ° C., 0.5 cm 3 of acetic acid and 0.5 cm 3 of ethanol, stirred for 15 minutes, filtered off the precipitate formed, concentrated to dryness by distillation under reduced pressure and obtained 5.7 g of crude title compound which was chromatographed on silica eluting with a hexane mixture and ethyl acetate (9/1) and gets

3.1 g of desired product.

  // D = +66.5 + 2.5 (c = 0.6%, chloroform).

  Example 6: (1 R, cis, E) 2,2-dimethyl-3-fluoro-3 (2,2,2-trifluoro) ethoxy-3-oxo-propenyl / cyclopropane carboxylate penta-1,4-diyn-3-yl: Step A: (1R, cis; E) 2,2-dimethyl-3/2-fluoro-2-carboxyethenyl / cyclopropane carboxylate penta 1,4-diyn-3-yl:

  5 g of (1R, cis; E) 2,2-dimethyl 3/2-fluoro are mixed together.

  Penta-1,4-diynyl 3-oxopropenyl / cyclopropane carboxylate, 500 mg of para-toluenesulphonic acid, 50 cm3 of toluene, refluxed until the end of isobutylene evolution (about 20 minutes), cooled, washed the toluene solution with water, concentrated to dryness by distillation under reduced pressure and obtained 4.1 g of desired product.

IR spectrum (chloroform).

  Absorption at 1705cm-1 attributed to C = O of the acid.

  Absorption at 1737 cm -1 attributed to C = 0 of the absorption Absorption at 1653 cm -1 attributed to C = C of geometry E.

  Absorptions at 3 300cm'l, 2130cm1-attributed to C = CH.

  Step B: (1 R, cis, E) 2,2-dimethyl-3-fluoro-3-chloro-2,2,2-trifluoro-ethoxy-3-oxo-propenyl) cyclopropane carboxylate penta-1,4-diyn-3-yl:

  2 g of product prepared in Stage A, 1.5 g of 2,2,2

  trifluoro ethanol, 15 cm3 of methylene chloride, cooled to 0 C introduced 100 mg of dimethylamino pyridine, cooled to 0OC and added a solution of 1.56 g of dicyclohexyl carbodiimide in 5 cm3 of methylene chloride, stirred for 3 hours at 20 ° C. C., the precipitate formed is filtered off, the filtrate is concentrated to dryness by distillation under reduced pressure and 4.3 g of crude title compound are obtained, which is chromatographed on silica, eluting with a mixture of hexane and isopropyl ether ( 9/1) and obtains 1.9 g of

desired compound.

  D = + 33.5 ± 2 (c = 0.4%, chloroform).

12 2570698

  EXAMPLE 7 (1R, cis, E) 2,2-dimethyl-3/2-fluoro-3-isopropyloxy-3-oxo-propenyl / cyclopropane carboxylate penta 1,4-diyn-3-yl: 2 g of (1R, cis) are mixed E) 2,2-dimethyl-3-fluoro-2-carboxy-ethenyl-cyclopropane carboxylate penta-1,4-diyn-3-yl, isopropane, 20 cm3 methylene chloride, 100 mg dimethylamino pyridine, cooled at 0 ° C., a solution of 1.56 g of dicyclohexyl carbodiimide in 5 cm 3 of methylene chloride is introduced, the mixture is stirred for 3 hours at 20 ° C., the insoluble matter formed is filtered off and the filtrate is concentrated to dryness by distillation under reduced pressure and 3.2 g of crude title compound is obtained, which is chromatographed on silica eluting with a mixture of hexane and isopropyl ether (9/1).

  and obtains 1.7 g of desired product.

  / I / D = + 43.5o + 1 (c = 1%, chloroform).

  EXAMPLE 8 Penta-1,4-dian-3-yl (1R, cis; Z) 2,2-dimethyl-3-oxo-3 (2,2,2-trifluoroethoxy) propenyl / cyclopropane carboxylate: Step A: ( 1R, cis; Z) 2,2-dimethyl-3/2-carboxyenhenyl / penta-1,4-diynyl-3-yl cyclopropane carboxylate: 2 g of (1R, cis; Z) 2,2-dimethyl-3-oxo are mixed Penta-1,4-diynyl 3-tert-butoxypropenyl / cyclopropane carboxylate, 200 mg of para-toluenesulphonic acid, 20 cm3 of toluene, refluxed the reaction mixture at 150 ° C. (outside temperature) until the end of evolution. isobutylene (about 15 minutes), cooled, washed with water, dried, concentrated to dryness by distillation under reduced pressure

  and obtains 1.6 g of desired product. F = 110OC.

  Step B: (1R, cis, Z) 2,2-dimethyl-3-oxo-3-2,2,2-trifluoro-ethoxy-propenyl-cyclopropane carboxylate penta-diyn-3-yl:

  1.6 g of the product prepared in Stage A, 2 g of 2,2,2

  trifluoro ethanol, 15 cm3 of methylene chloride, cooled to 0 C, introduced 50 mg of dimethylamino pyridine, then a soluton of 1.3 g of dicyclohexylcarbodiimide in 5 cm3 of methylene chloride, stirred for 16 hours at 20C, removed by filtration the precipitate formed, the filtrate is concentrated to dryness by distillation under reduced pressure to give 4 g of the crude title compound which is chromatographed on silica eluting with a mixture of hexane and

  of ethyl acetate (9/1) and gives 1.8 g of the desired compound.

  / "/ D = + 47a + 1.5 (c = 1%, chloroform).

  Insecticidal study of the compounds of the invention: The test insects are female houseflies aged 4 days; it is carried out by direct spraying at a concentration of 1 g or 0.1 g / l in a chamber of Kearns and March using as solvent

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  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. The experimental results obtained are summarized in the following table: Compounds of Example KT in mn Concentration 1 1.5 1 g 3 5.1 1 g 4 3.2 0.1 g 3.8 1 g 7 4.8 0 Example 9: Preparation of a soluble concentrate: A homogeneous mixture of: Product of Example 4 .................. .............. 0.25 g Piperonyl butoxide.

  ............................. 1.00 g Tween 80 ............... .............. DTD: ................. 0.25 g Topanol A ........... ............................. DTD: ..... 0,1 g Water ......... .......................................... 98.4 g Example 10: Preparation of an emulsifiable concentrate: intimately mixed: Product of Example 4 ................................ 0.005 g Piperonyl butoxide ................................ 0.05 g Topanol A ... DTD: .... ...................................... 0.1 g Tween 80 ...... ........... DTD: ............................. 3.5 g Xylene ... ............................. DTD: ................ 96,345 g Example 11: Preparation of an Emulsifiable Concentrate: A homogeneous mixture is carried out of: Product of Example 7 .... DTD: ...................... ...... 10 g Tween 80 ................................ DTD: ...... ........ 15 g Topanol A ...................................... ....... DTD: 0.5 g Xylene .................................... ............ 74.5 g Example 12: Preparation of a Smoke Composition: Homogeneously Mixed: Product of Example 1 ........................... ..... 0, 25 g Tabu powder ...................................... .. 25.00 g Cedar leaf powder ............................ 40.00 g 14 z 7 U2570698 Wood powder of pine ................................. 33,75 g Bright green ......... ................................ 0.5 g pnitrophenol ............. ............................ 0.5 g..DTD: 2570698

R E V E N D I C AT IO N S

  1.- The compounds corresponding to the general formula I:

H3C CH3

R3 C02CH-C-CR1 (I)

C _ CR2

  in which R1 and R2 are identical or different from one another and represent a hydrogen atom or an alkyl radical containing from 1 to 8 carbon atoms, and: - or R3 represents a radical:

R4. / _

R4 - H

c = c

RZOC

  in which the geometry of the double bond is E or Z and wherein R4 represents a hydrogen atom, or a fluorine, chlorine or bromine atom, or an alkyl or alkoxyl radical containing from 1 to 8 carbon atoms, Z represents an oxygen or sulfur atom and R represents: either a linear, branched or cyclic alkyl radical, saturated or unsaturated, containing from 1 to 18 carbon atoms, optionally 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 a

  or more identical or different functional groups.

- or R3 represents a radical:

R5A / H

C = C

N- = C /

  in which A represents an oxygen or sulfur atom, a sulfoxide group or a sulfone group and,

16 2570698

  - or R5 represents a linear alkyl radical branched or cyclized, saturated or unsaturated, containing up to 18 carbon atoms, the chain may be interrupted by one or more hetero atoms, and or substituted by one or more halogen atoms, - Or R5 represents an aryl or aralkyl radical containing up to 18 carbon atoms, or Rt represents a radical: Hal l C = C_NEC / in which Hal represents a halogen atom, under all

  possible stereoisomeric forms as well as all stereoisomeric mixtures

possible isomers.

  2 - The compounds of formula I as defined in claim 1

  in which R1 and R2 represent a hydrogen atom.

  3 - The compounds of formula I as defined in claim 1 or 2 in which R3 represents a radical:

R4 H

  1 C C = C R02C / in which the geometry of the double bond is E, or Z, R and R4

  retaining the same meaning as before.

  4 - The compounds of formula I as defined in claim 3, in which R represents a linear alkyl radical, or branched

  containing 1 to 8 carbon atoms.

  The compounds of formula I as defined in claim 4 in which R represents a methyl, ethyl, isopropyl or terbutyl radical. 6 - The compounds of formula I as defined in claim 4, in which R represents an alkyl radical containing from 1 to 8 atoms

  of carbon substituted with one or more halogen atoms.

  7 - The compounds of formula I as defined in claim 6 in which the radical R is substituted by one or more atoms

of fluorine.

  8 - The compounds of formula I as defined in claim 7 in which R represents a radical -CH2CF3

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  The compounds of formula I as defined in any one of

  Claims 3 to 8 in which R4 represents a hydrogen atom,

  in which the geometry of the double bond is Z, and the structure

  of the cyclopropane copula is 1R, cis.

  Compounds of formula I as defined in any one of

  Claims 3 to 8 in which R4 represents an atom of

  fluorine, chlorine or bromine and in which the geometry of the double

  bond is E and the structure of the cyclopropane copula is 1R, cis.

The compounds of formula I as defined in claim 10

  in which R4 represents a fluorine atom.

  12 - Process for the preparation of the compounds of formula I as defined in

  any of claims 1 to 11, characterized in that one

subject an acid of formula II:

H3C.CH3

S I (II)

R3 C02H

  in which R3 retains its previous meaning, or a functional derivative of this acid, with the action of an alcohol of formula: CCR1

HO-CH (III)

  C-CR 2 wherein R 1 and R 2 retain their previous meaning, or a functional derivative of this alcohol, to obtain the compound of

corresponding formula I.

  13 - Application of the compounds of formula I as defined in one

  Claims 1 to 11, the fight against plant pests

and parasites of the premises.

  14 - Compositions for combating 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 any one of the claims

1 to 11.

  - The insecticidal compositions containing as active principle at least one of the products defined in any one of the

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Claims 1 to 11.

  16 - The acaricide compositions containing as active principle the

  least one of the products defined in any one of the claims

1 to 11.

  17 - The nematicidal compositions containing as active ingredient the

  least one of the products defined in any one of the claims

1 to 11.

  - Acaricidal compositions for the control of parasites of warm-blooded animals, especially against ticks and scabies, characterized in that they contain as active principle, at least one of the products defined in any one of the

Claims 1 to 11.

  19 - Compositions intended for animal feed containing as active ingredient at least one of the products defined in one

  any of claims 1 to 11.

  - Compositions endowed with insecticidal activity, acaricide or nematicide, characterized in that they contain as active ingredient, on the one hand at least one of the compounds of general formula (I) and on the other hand, at least one of pyrethroid esters chosen in

  the group consisting of esters of allethrolones, alcohol 3,4,5,6-

  methyl tetrahydrophthalimide, 5-benzyl-3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and o-cyano-3-phenoxy alcohols

  benzyl chrysanthemic acids, by alcohol esters 5-

  Methyl benzyl 3-furyl 2,2-dimethyl-3- (2-oxo-3-tetracyl)

  hydrothiophenylidene methyl) cyclopropane-1-carboxylic acid, by the esters of 3-phenoxy benzyl alcohol and alcohols "-cyano 3-phenoxy

  Benzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane

  1-carboxylic acid esters of 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylic acid-cyano-3-phenoxy benzyl alcohols,

  by the 3-phenoxybenzyl alcohol esters of 2-

  parachlorophenyl 2-isopropyl acetic acid esters of allethrolones, 3,4,5,6-tetrahydrophthalimido methyl alcohol, 5-benzyl 3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and "cyano" alcohols

  3-phenoxy benzyl acids 2,2-dimethyl-3- (1,2-2,2-

  tetrahaloethyl) cyclopropane-1-carboxylic acid, in which "halo"

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  represents a fluorine, chlorine or bromine atom, it being understood that the acidic copulas and alcohols of the pyrethroid esters above

  can exist in all their possible stereoisomeric forms.

  21 - The compositions and associations according to any of the

  claims 14 to 20 characterized in that they contain, in

  in addition, a pyrethroid synergist.