IE51451B1

IE51451B1 - Cyclopropane carboxylic acid derivatives,their preparation,their use in the control of parasites of plants,animals and localities,compositions containing them and new intermediates obtained

Info

Publication number: IE51451B1
Application number: IE1479/81A
Authority: IE
Original assignee: Roussel Uclaf
Priority date: 1980-07-02
Filing date: 1981-07-01
Publication date: 1986-12-24
Also published as: DK163875C; ES8301198A1; FI78066B; OA06849A; DK306290D0; IE811479L; EG15179A; JPH01156943A; ES8305301A1; JPS6023342A; EP0048186B1; JPS6254420B2; AU3610084A; FR2486073B1; ES503595A0; BR8104222A; FR2539956B2; JPH0417941B2; EP0048186A2; ATE13054T1

Abstract

1. Claims for the Contracting States : BE CH DE FR GB IT LI LU NL SE In all the possible isomeric forms or in the form of mixtures, the compounds with the formula (I') see diagramm : EP0048186,P72,F1 in which the cyclopropane copula is of IR cis structure and the double bond is of Z geometry and in which A' represents either an alkyl radical containing from 1 to 18 carbon atoms or a benzyl radical possibly substituted by one or more radicals chosen from the group composed of the alkyl radicals containing from 1 to 4 carbon atoms, the alkenyl radicals containing from 2 to 6 carbon atoms, the alkenyloxy radicals containing from 2 to 6 carbon atoms, the alkadienyl radicals containing from 4 to 8 carbon atoms, the methylene dioxy radical and halogen atoms, or a group see diagramm : EP0048186,P72,F2 in which the substituent R1 represents a hydrogen atom or a methyl radical and the substituent R2 a monocyclic aryl radical or a group -CH2 -C -= CH or a group see diagramm : EP0048186,P72,F3 in which a represents a hydrogen atom or a methyl radical and R3 represents the radical -CH2 -CH=CH2 , -CH2 -CH=CH-CH3 , -CH2 -CH=CH-CH=CH2 , CH2 -CH=CH-CH2 -CH3 , or a group see diagramm : EP0048186,P72,F4 in which a represents a hydrogen atom or a methyl radical, R3 retains the same significance as previously, R'1 and R'2 , being 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, an alkyloxy-carbonyl group including from 2 to 5 carbon atoms, or a cyano group, or a group see diagramm : EP0048186,P72,F5 in which B represents an oxygen or sulphur atom or a group see diagramm : EP0048186,P73,F1 or -CH2 - and R4 represents a hydrogen atom, a -C -= N radical, a methyl radical, a -CONH2 radical, a -CSNH2 radical or a -C -= CH radical, R5 represents a halogen atom or a methyl radical and n represents a number 0, 1 or 2, or a group see diagramm : EP0048186,P73,F2 or a group see diagramm : EP0048186,P73,F3 in which the substituents R6 , R7 , R8 , R9 represent a hydrogen atom, a chlorine atom, or a methyl radical and in which S/l symbolises an aromatic ring or a similar dihydro or tetrahydro ring, or a group see diagramm : EP0048186,P73,F4 or a group see diagramm : EP0048186,P73,F5 in which R10 represents a hydrogen atom or a radical CN, R12 represents a radical -CH2 - or an oxygen atom, R11 represents a thiazolyl or a thiadiazolyl radical, of which the bond with -CH-/R10 can be found at any one of the available positions R12 being attached to R11 by the carbon atom included between the sulphur atom and a nitrogen atom, or a group see diagramm : EP0048186,P73,F6 or a group see diagramm : EP0048186,P73,F7 in which R13 represents a hydrogen atom or a radical CN, or a group see diagramm : EP0048186,P74,F1 in which R13 is defined as above, and the benzoyl radical is in position 3 or 4, or a group see diagramm : EP0048186,P74,F2 in which R14 represents a hydrogen atom, a methyl, ethynyl or cyano radical and R15 and R16 , are different and represent a hydrogen, fluorine or bromine atom, or a group see diagramm : EP0048186,P74,F3 in which R14 is defined as above, each of the R17 's represents independently an alkyl group containing from 1 to 4 carbon atons, an alkoxy group containing from 1 to 4 carbon atoms, an alkylthio group containing from 1 to 4 carbon atoms, an alkylsulphonyl group containing from 1 to 4 carbon atoms, a trifluoromethyl, 3,4-methylenedioxy, chloro, fluoro or bromo group, p represents a numeral 0, 1 or 2, and B' represents an oxygen atom or a sulphur atom and R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted by one or more identical or different groups chosen from the group constituted by the halogen atoms, the OH or SH groups, the OR' or SR' groups in which R' represents an alkyl radical containing from 1 to 8 carbon atoms, the groups NO2 or see diagramm : EP0048186,P74,F4 in which R" and R'", being identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 8 carbon atoms, the groups C -= N, SO3 H or PO4 H2 or the groups COalk1 , SO2 alk2 , or SO3 alk3 in which alk1 , alk2 and alk3 represent alkyl radicals containing from 1 to 18 carbon atoms or R represents an alkyl radical containing from 1 to 18 carbon atoms substituted by an aryl radical, itself possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 18 carbon atoms, by one or more CF3 , OCF3 SCF3 , or by a group (G) : see diagramm : EP0048186,P74,F5 or R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted on two adjacent carbons by a group (G1 ) see diagramm : EP0048186,P74,F6 or substituted by a group see diagramm : EP0048186,P75,F1 or R represents an aryl group containing from 6 to 14 carbon atoms, possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 8 carbon atoms or by a CF3 , OCF3 or SCF3 group, or R represents a pyridinyl, furanyl, thiophenyl, oxazolyl or thiazolyl radical. 1. Claims for the Contracting State : AT Process for preparing in all the possible isomeric forms or in the form of mixtures, the compounds with the formula (I') see diagramm : EP0048186,P82,F3 in which the cyclopropane copula is of IR cis structure and the double bond of Z geometry and in which A' represents either an alkyl radical containing from 1 to 18 carbon atoms or a benzyl radical possibly substituted by one or more radicals chosen from the group constructed by the alkyl radicals containing from 1 to 4 carbon atoms, the alkenyl radicals containing from 2 to 6 carbon atoms, the alkenyloxy radicals containing from 2 to 6 carbon atoms, the alkadienyl radicals containing from 4 to 8 carbon atoms, the methylene dioxy radical and halogen atoms, or a group see diagramm : EP0048186,P82,F4 in which the substituent R1 represents a hydrogen atom or a methyl radical and the substituent R2 a monocyclic aryl or a -CH2 - C -= CH group, or a group see diagramm : EP0048186,P82,F5 in which a represents a hydrogen atom or a methyl radical and R3 represents the radical -CH2 -CH=CH2 , -CH2 -CH=CH-CH3 , -CH2 -CH=CH-CH=CH2 , CH2 -CH=CH-CH2 -CH3 , or a group see diagramm : EP0048186,P82,F6 in which a represents a hydrogen atom or a methyl radical, R3 retains the same significance as previously, R'1 and R'2 , being 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, an alkyl-oxycarbonyl group containing from 2 to 5 carbon atoms, or a cyano group, or a group see diagramm : EP0048186,P83,F1 in which B represents an oxygen or sulphur atom or a group see diagramm : EP0048186,P83,F2 or -CH2 - and R4 represents a hydrogen atom, a -C -= N radical, a methyl radical, a -CONH2 radical, a -CSNH2 radical or a -C -= CH radical, R5 represents a halogen atom or a methyl radical and n represents a numeral 0, 1 or 2, or a group see diagramm : EP0048186,P83,F3 or a group see diagramm : EP0048186,P83,F4 in which the substituents R6 , R7 , R8 , R9 represent a hydrogen atom, a chlorine atom, or a methyl radical and in which S/l symbolises an aromatic ring or a similar dihydro or tetrahydro ring, or a group see diagramm : EP0048186,P83,F5 or a group see diagramm : EP0048186,P83,F6 in which R10 represents a hydrogen atom or a CN radical, R12 represents a -CH2 - radical or an oxygen atom, R11 represents a thiazolyl or a thiadiazolyl radical, of which the bond with -CH-/R10 can be found at any one of the available positions, R12 being attached to R11 by the carbon atom included between the sulphur atom and a nitrogen atom, or a group see diagramm : EP0048186,P84,F1 or a group see diagramm : EP0048186,P84,F2 in which R13 represents a hydrogen atom or a CN radical, or a group see diagramm : EP0048186,P84,F3 in which R13 is defined as above, and the benzoyl radical is in position 3 or 4, or a group see diagramm : EP0048186,P84,F4 in which R14 represents a hydrogen atom, a methyl, ethynyl or cyano radical and R15 and R16 , which are different, represent a hydrogen atom, a fluorine or a bromine atom, or a group see diagramm : EP0048186,P84,F5 in which R14 is defined as above, each of the R17 's represents independently an alkyl group containing from 1 to 4 carbon, an alkoxy group containing from 1 to 4 carbon atoms, an alkylthio group containing from 1 to 4 carbon atoms, an alkylsulphonyl group containing from 1 to 4 carbon atoms, a trifluoromethyl, 3,4-methylenedioxy, chloro, fluoro or bromo group, p represents a numeral 0, 1 or 2 and B' represents an oxygen atom or a sulphur atom and R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted by one or more identical or different functional groups chosen from the group constituted by the halogen atoms, the OH or SH groups, the OR' or SR' groups in which R' represents an alkyl radical containing from 1 to 8 carbon atoms, the NO2 or see diagramm : EP0048186,P84,F6 groups in which R" and R'", which are identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 8 carbon atoms, the groups C -= N, SO3 H or PO4 H2 groups or the COalk1 , SO2 alk2 , or SO3 alk3 groups in which alk1 , alk2 and alk3 represent alkyl radicals containing from 1 to 18 carbon atoms, or R represents an alkyl radical containing from 1 to 18 carbon atoms substituted by an aryl radical, itself possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 8 carbon atoms, by one or more CF3 , OCF3 SCF3 , or by a group (G) : see diagramm : EP0048186,P85,F1 or R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted on two adjacent carbons by a group (G1 ) see diagramm : EP0048186,P85,F2 or su

Description

The present invention relates to new derivatives of cyclopropane carboxylic acid, their preparation, their use in the control of parasites of plants, of anting Ta and of localities, the compositions containing them and the new intermediates obtained.

The subject of the invention is, in all the possible isomeric forms or in the form of mixtures, the compounds of formula (I1): eo2c CH (I') in which the cyclopropane moiety is of 1R cis structure and'-the double bond is of Z geometry and in which A' represents " either 311 radical containing from 1 to 18 carbon. atoms, - or a benzyl radical possibly substituted by one or more radicals selected from the group constituted by the alkyl radicals containing from 1 to 4 carbon atoms, the alkenyl radicals containing from 2 to 6 carbon atoms, the alkenyloxy radicals containing from 2 to 6 carbon atoms, the alkadienyl radicals containing from 4 to 8 carbon atoms, the methylene dioxy radical and the halogen atoms, or a groups CHgSg in which the substituent represents a hydrogen atom 10 or a methyl radical and the substituent Hg represents a monocyclic aryl or a group -CHg-CmCH and especially a -benzyl 5-furyl methyl group, - or a group: in which a. represents a hydrogen atom or a methyl radical 15 and represents the radical -CHj-CiKHj, -CH2-CH.CH-CH5, -CH2-CH«CH-CH-CH2 or -CH^CH-CH-CHg-CHj, - 3 - or a group: in which a represents a hydrogen atom or a methyl radical, B^ keeps the same meaning as before and E'^ and E'2, being the same or different, represent a hydrogen atom, a halogen atom, an alkyl raiic'al eontaining from 1 to 6 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms, an alkyloxjcarbonyl group containing from 2 to 5 carbon atoms or a cyano group, - or a group: in which B represents an oxygen or sulphur atom or a group 1( . —C— or -CH2- and E^ represents a hydrogen atom, a radical -CsH, a methyl radical, a radical -0011021 a radical -CSHHg or a radical -Cs CH, represents a halogen atom or a methyl radical and n represents a number equal to 0, 1 or 2, and especially the 3-phenoxy benzyl, α-cyano 3-phenoxy benzyl, α-ethynyl 3-phenoxy benzyl, 3~benzoyl benzyl, l-(3~phenoxyphenyl) ethyl or α-thioamido 3-phenoxy benzyl group, - or a group: in which the substituents Εθ, E?, Eg and Εθ represent a hydrogen atom, a chlorine atom or a methyl radical and in which S/I symbolises an aromatic ring or an analogous dihydro or tetrahydro ring, - or a group: •5 - or a group: in which R^q represents a hydrogen atom or a radical CN, ^12 represents a radical - GHg - or an oxygen atom and B11 represents a thiazolyl or thiadiazolyl radical of which 5 the bond with R1Q can be at any one of the available - CH positions, R^2 being bonded to R^ hy the carbon atom included between the* sulphur atom and a nitrogen atom, - or a group: η or a group: -CH R. in which R^ represents a hydrogen atom or a radical CN, - or a group: CH- in which E^ is defined as above and the benzyl radical in which E^ represents a hydrogen atom or a methyl, ethynyl or cyano radical and E^ and E-^g, being different, represent a hydrogen, fluorine or bromine atom, - or a group: in which is defined as above, each of the E^'s represents independently an alkyl group containing from 1 to 4 carbon atoms, an alkoxy group containing from 1 to 4 carbon atoms, an alkylthio group containing from 1 to 4 carbon atoms, an alkyl sulphonyl group containing from 1 to 4 carbon atoms, 5115 1 a trifluoromethyl, 3,4-methylenedioxy, chloro, fluoro or bromo group, p represents a number equal to 0, 1 or 2 and B' represents an oxygen atom or a sulphur atom and E represents an alkyl radical containing from 1 to 18 ς carbon atoms substituted by one or more identical or 2 1 differentl groups chosen from halogen atoms, the OH and SH groups, the OR' and SR* groups in which R' represents an alkyl radical containing from 1 to 8 carbon atoms, R the groups NO, or -N in which R and R"1, being z R' identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 8 carbon atoms, the groups C=N, SO^H and PO^H2and 9rouPs COalk^, SO2alk2 and SO3alk3 in which alk1, alk2 and alk3 represent alkyl radicals containing from 1 to 18 carbon atoms, or R represents an alkyl radical containing from 1 to 18 carbon atoms substituted by an aryl radical, itself possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 8 carbon atoms, by one or more CF3, OCF3 or SCF3 groups, or by a group (G): /C\ Ο H (G) or R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted on two adjacent carbons by a group (G1) •°\ /H (G,l or substituted by a group 0- or R represents an aryl group containing from 6 to 14 carbon atoms, possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 8 carbon atoms or by a CF3, OCF3 or scf3 group, or R represents a pyridinyl, furanyl, thiophenyl, oxazolyl or thiazolyl radical.

The compounds of formula (I') may exist in stereoisomeric forms where there are one or more centres of asymmetry in A and/or R.

When A represents an alkyl radical, this is preferably the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl radical.

When A represents a benzyl radical substituted by one or more alkyl radicals, this is/these are preferably the methyl or ethyl radical(s).

When A represents a benzyl radical substituted by one or more alkenyl radicals, this is/these are preferably the vinyl, allyl, 2-methylallyl or isobutenyl radical(s).

When A represents a benzyl radical substituted, by 451 one or more alkenyloxy radicals, this is/these are preferably the vinyloxy, allyloxy, 2-methylallyloxy or isobutenyloxy radical(s).

When A represents a benzyl radical substituted by one or more halogen atoms, this is/these are preferably the chlorine, bromine or fluorine atom(s).

When R represents an alkyl radical substituted by one or more functional groups, there is understood preferably by alkyl a radical containing from 1 to 8 carbon atoms such as, for example, the methyl, ethyl, -propyl, isopropyl, n-butyl, isobutyl or tert-butyl radical.

When R represents an alkyl radical substituted by one or more functional groups, there is understood preferably by functional group a halogen atom, a group OH or SH,. a group OR' or SR* in which R' represents an alkyl radical containing from 1 to 8 carbon atoms, y a group NO2 or Ir in which R.and R', being the \gn , same or different, represent a hydrogen atom or an alkyl radical containing from 1 to 8 carbon atoms, a group 0 s H, SO^H or FO4H2 or a group CO alk p SOgalkp or SO^alkj in which alkj, alkj and alkj represent alkyl radicals containing from 1 to 18 carbon atoms.

R can also represent an alkyl radical substituted by an aryl radical such as, for example, the benzyl radical or the phenethyl radical, itself possibly substituted by one or more groups OH, Oalk or alk containing from 1 to 8 carbon - 9 atoms, by one or more groups CF^, OCF^ or SCF^, or by a group (G): (G) E can also represent an alkyl radical substituted on two adjacent carbons by a group (G^): (¾) When S represents an alkyl radical substituted by one or more functional groups, there may be mentioned as preferred·values of E the radicals: -(CH2)n-C Halj in which n is an integer from 1 to 8 and Hal is a halogen atom, for example the radical -CHg-CCl^, -CH2-CF5, -CH2-CH2-CC15 or -CHg-CHj-CF^, -(CHg)^ -CH Hal2 in which Hal is defined as above and Π| is a number from 0 to 8, for example the radical -CH2-CKC12, -CH2-CHF2 or -CHF2, -(CH2)n-CH2 Hal in which n and Hal are defined as above, for example the radical -CH2-CH2C1 or -CHg-CH^, -C-iCHalj)^ in which Hal is defined as above, for CP5 example the radical -G-(CF^)j or -C^— CF^ 'Xci, CF, -C<—CH, CF, CF, / 5· -c_ch5 xch3 .CF, or -C<^—CH CH2-CH5 CF, -C-CH, .CF, or -C — CF, CH, -X-OT Xch3 X 5 -C-CT or -(CE2)£CT, in which n is defined as before, CHal, / 5 -C—CN , in which Hal is defined as before, ^H CCl, for example the radical -C—CT , ^H -(CH2)gOB', in which n is defined as before and.

B1 represents a hydrogen atom or a straight or branched alkyl radical containing from 1 to 8 carbon atoms, for example the radical -CHg-OCH^, -CHg-CHg-O-CHj, -CH^CH^O-CHj-CH^ or -CHg-CHg-OH, (CH. in which n and E1 are defined as before E' and the two radicals E' can be different from each other, .CH example the radical -CHg-CHg-lr ' , for CH, -ch2-ch2-n· or -CH2-CH2-N /H3 CH, ch2-ch3 -(CH2)n-j3H-CH2, in which n is defined as H-C'^CH, 3 before, for example the radical ~CH2-CH-CH2, ° i HjC^^CHj -(CH~) -CH—CHO , in which n is defined as before, for 2 n | - 2 OH OH example the radical -CH2-CH-CH2 OH ,-OH -(CH2)-< in which n is defined as before, for example the radical -CHg-O -((¾ r\ or -CH2~CH2-0—i , in which n is defined as before, for . example the benzyl or phenethyl radical, and -(οη2)„ ΖΛ , in which η is defined as before, for example the radical When H represents a possibly-substituted aryl radical this is preferably the phenyl radical or the phenyl radical substituted by one or more groups OH, Oalk or alk, containing from 1 to 8 carbon atoms, or by a group CF^, OCF^ or SCFy The subject of the invention is, especially, the compounds of formula (I') as defined before, corresponding to the formula (I): (1) in which the cyclopropane moiety is of 1R cis structure and the double bond is of Z geometry and in which A represents - either an alkyl radical containing from 1 to 18 carbon 15 atoms, - or a possibly-substituted benzyl radical as defined before, - or a group: -CH. in which a and are defined as before, - or a group: in which-a, R'p H'g and are defined as before, - or a group: H Ο II in which B represents an oxygen atom, a group -Cor -CHg-, defined as before, R^ represents a chlorine atom or a methyl radical and n represents a number equal to 0,1 or 2, and especially the 5-phenoxy benzyl, a-cyano 5"phenoxy benzyl or α-ethynyl 3-phenoxy benzyl group, or a group: - or a group: CS - or a group: In which the substituents Βθ, Β?, Βθ, Βθ and. S/I are defined as before, and B is defined as before.

The subject of the invention is, especially, the compounds of formula (I1) as defined before, in which A represents an a-cyano-3-phenoxy-benzyl group in S, B or BS form as well as those in which A1 represents a 2-methyl-4-oxo-3-(2-propenyl)-2-cyclopenten-l-yl group in S, B or BS form.

The subject of the invention is, more especially, the compounds of formula (I') for which B represents an alkyl radical containing from 1 to 18 carbon atoms, substituted by one or more functional groups as defined above, and especially those in which B represents an alkyl radical substituted by one or more halogen atoms, for example one or more fluorine atoms. As an example of an alkyl radical substituted by one or more halogen atoms there may be mentioned especially the radical -CHgCF^.

The subject of the invention is in particular the compounds of which the preparation is given further on in the experimental part and especially, among these, the compounds of Examples 1, 2, 25, 26, 29, 50 and 55· The compounds of formula (I'). show interesting properties which enable them to be used in the control of parasites which can be, for example, the control of parasites of plants, the parasites of premises and the parasites of warm-blooded animals. Thus the products of the invention can be used to control insects, nematodes and acaridae which are parasites of plants and of animals.

The subject of the invention is, therefore, the use of the compounds of formula (I1) in the control of parasites of plants, parasites of premises and parasites of warm-blooded animals.

The products of formula (I1) can therefore be used especially to control insects in the agricultural sphere, to control, for example, aphides, the larvae of lepidoptera and coleoptera. They are used at doses included between ' 10 g and 500 g of active substance per hectare.

The products of formula (I1) can also be used to control insects in premises , to control especially flies, mosquitoes and. cockroaches.

The compound of Example 1 is a quite remarkable product as the results of the tests hereinafter show.

It displays excellent lethal capacity and very good knock-down capacity.

The products of formula (I') are, in addition, stable to light and are not toxic to mammals.

All these properties make of the products of formula (I') products which correspond perfectly to the requirements of the modem agro-chemical industry: they enable the crop to be protected whilst preserving the environment.

The products of formula (I') can also be used to control acaridae and nematodes which are parasites of plants.

The compounds of formula (I1) can also be used to control acaridae which are parasites of animals, to control, for example, ticks and especially ticks.of the species Boophilus;, those of the species Hyalomnie, those of the species Amblyomnia and those of the·species Ehipicephalus, or to control all kinds of scabies and especially the sarcoptic scabies, the psoroptic scabies and the chorioptic scabies.

The subject of the invention is, therefore, also the compositions intended to control parasites of warmblooded animals, parasites of premises and of plants, characterised in that they contain at least one of the products defined above.

The subject of the invention is, especially, the insecticidal compositions containing, as active principle, at least one of the products defined above.

Among the preferred compositions, especially the insecticidal compositions, of the invention there may be mentioned especially the compounds containing (S) a-cyano3-phenoxy-benzyl (IE cis) 2,2-dimethyl-3((Z) 3(2,2,2-trifluoroethoxy)-3-oxo -l-propenyll-cyclopropane-carboxylate, (S) a-cyano-J-phenoxy-benzyl (IB cis) 2,2-dimethyl-3C(Z)~ 3-oxo-3-(2-(1,1,1,5,5,3-hexafluoro)-propoxy)-1-propenyl]cyclopropane-carboxylate, (E) a-ethynyl-3-phenoxy-benzyl (IE cis) 2,2-dimethyl-3C(S)* 3-oxo-3-(2,2,2-trifluoroethoxy)-1-propenyl]-cyclopropane carboxylate, (ES) cyano-6-phenoxy-2-pyridyl-methyl (IE cis) 2,2-dimethyl3((Z)-5-oxo-3~(2,2,2-trifluoroethoxy)-1-propenyl]-cyclopropane- carboxyiate, (S) a-cyano-3-phenoxy-benzyl (IE cis) 2,2-dimethyl-3.((Z)3-0x0-3"(2-fluoroethoxy)-1-propenyl]-cyclopropane carboxyiate, (3-propargyl-2,5-dioxoimidazolidinyl)-methyl (IE cis) 2,2-dimethyl-3t(Z) 3-oxo-3-(2,2,2-trifluoroethoxy)-1-propenyl] cyclopropane-carboxyiate and (IS) 2-methyl-4-oxo-3-(2-propenyl)-2-cyclopenten-l-yl (IE cis) 2,2-dimethyl-3C(Z) 3-oxo-3-(2,2,2-trifluoroethoxy)1-propenyl]-cyclopropane-carboxyiate.

These compositions are prepared according to the usual processes of the agro-chemical industry or of the veterinary industry or of the industry of products intended for animal feeding.

In these compositions intended for agricultural use and for use in premises the active substance or substances have added to it/them possibly one or more other pesticidal agents. These compositions can be presented in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible· strips, baits or other preparations normally employed for the use of this kind of compound.

In addition to the active principle, these compositions contain, in general a vehicle and/or a non-ionic surfaceactive agent ensuring, in addition, uniform dispersion of the substances constituting the mixture. The vehicle used can be a liquid such as water, alcohol, the hydrocarbons or other organic solvents, or a mineral, animal or vegetable oil, a powder such as talc, clays, silicates or kieseiguhr or a combusible solid.

The insecticidal compositions according to the invention contain, preferably, from 0.005% to 10% by weight of active substance.

According to an advantageous modus operandi, for use in premises the compositions according to the invention are used in the form of fumigating compositions.

The compositions according to the invention can then be can advantageously constituted, for the non-active part, by a combustible insecticidal coil, or else by an incombustible fibrous substrate. In the latter case the fumigant obtained after incorporation of the active substance is placed on a heating apparatus such as an electric mosquito destroyer. In the case in which an insecticidal coil is used the inert support can be, for example, composed of pyrethrum marc, Tabu powder (or powder of Machilus Thumbergii leaves), pyrethrum-stem powder, cedar-needle powder, wood dust (such as pine sawdust), starch and coconut shell powder.

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

In the case in which an incombustible fibrous support is used the dose of active substance can-then be, for example, from 0.03 to 9% by weight.

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

The concentration of active principle incorporated in the oil is preferably from 0.03 to 9% by weight.

The insecticidal compositions according to the invention, like the acaricidal and nematocidal compositions can have added to them possibly one or more other pesticidal agents. The acaricidal and nematocidal compositions can be presented especially in the form of powder, granules, suspensions, emulsions and solutions.

For acarieial use preferably wettable powders are used, for foliar spraying, containing from 1 to 80% or liquids for foliar spraying containing from 1 to 500 g/1 of active principle. Powders for foliar spraying can also be used containing from 0.05 to 5% of active material.

For nematocidal use preferably liquids for soil treatment are used containing from 300 to 500 g/1 of active principle.

The acaricidal and nematocidal compounds according to the invention are used, preferably at doses included between 1 and 100 g of active substance per hectare.

In order to increase the biological activity of the products of the invention they may be added to standard synergists used in such a case such as l-(2,5,8-trioxadodecyl)"2-propyl-4,5-methylenedioxy-benzene (or piperonyl butoxide) or N-(2-ethyl-heptyl)-bicyclo[2,2-l]5-heptene-2,3-di-carboximide, or piperonyl-bis-2-(2'-n-butoxy-ethoxy)ethylacetal (or tropital).

When it is a question of controlling acaridae which are parasites of animals, very often the products of the invention are incorporated in feeding compositions in association with a nutrient mixture adapted for animal feeding. The nutrient mixture can vary according tc the animal species and it can contain cereals, sugars and grains, soya bean-, peanut- and sunflower-cakes, meals of animal origin for example fish meals, synthetic amino acids, mineral salts, vitamins and antioxidants. 14 3 1 The subject of the invention is, therefore, the feeding compositions defined above.

The compounds of formula (I') show excellent general tolerance and the subject of the invention is, therefore, also the products of formula (I1), as medicaments, to control especially diseases caused by ticks and scabies.

The medicaments of the invention can be used both in human medicine and in veterinary medicine.

The medicaments of the invention are used especially 10 in human medicine to control lice as a preventive or curative agent and to control scabies. They can also be used as anthelmintics.

The medicaments of the invention can be administered externally by vaporisation, by shampooing, by bathing or painting-on.

The medicaments of the invention for veterinary use can also be administered by painting on to the dorsal spine according to the method called pour-on method.

They can also be administered by digestive or parenteral route.

The subject of the invention is, therefore, pharmaceutical compositions containing as active principle at least one of the medicaments defined above.

It may also be pointed out that the products of the 25 invention can be used as biocides or as growth-regulants.

The subject of the invention is also associations endowed with insecticidal, acaricidal or nematocidal activity, characterised in that they contain as active substance on the one hand one at least of the compounds of general formula (I1) and on the other hand one at least of the pyrethrinoid esters selected from the group constituted hy the esters of allethrolone , of 3,4,5,6-tetrahydrophthalimido methyl alcohol, of J-benzyl- 3-furyl-methyl alcohol, of 3-phenoxy-benzyl alcohol and of α-cyano-3-phenoxy-benzyl alcohol of chrysanthemio acids·, by the esters of 5-benzyl3-fttryl-methyl alcohol of 2,2-dimethyl-3-(2-oxo-3-tetrahydrothiophenylidene-methyl)-cyclopropane-l-carboxylic acid ; by the esters of 3-phenoxy-benzyl alcohol and of a-cyano-3-phenoxy-benzyl alcohol of 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylic acid. ; by the esters of α-cyano-3-phenoxy-benzyl alcohol, of 2,2-dimethyl3-(2,2-dibromovinyl)-cyclopropane-1-carboxylic acid;; by the esters of 3-phenoxy-benzyl alcohol of 2-parachlorophenyl 2- isopropyl-acetic acid ; by the esters of allethrolone , of 3»4,5i6-tetrahydrophthalimidomethyl alcohol, of 5-benzyl3- furyl-methyl alcohol, of 3-phenoxy-benzyl alcohol and of α-cyano-3-phenoxy-benzyl alcohol of 2,2-dimethyl 3-(1,2,2,2-tetrahalo)-eyelopropane-1-carboxylic acids, in which halo represents a fluorine, chlorine or bromine atom, it being understood that the compounds (I1) can exist in all their possible stereoisomeric forms the same as the acid and alcohol moieties of the pyrethrinoid esters above.

The associations according to the invention are especially of interest either in permitting control, through the polyvalence of their activity, of a more extensive range of parasites or in displaying, in certain cases, a synergistic effect.

The subject of the invention is also a process for preparing the compounds of formula (I*)» characterised in that an acid of formula (II): eo2c-ch A'OH (III) in which A' keeps the same meaning as before, to obtain 15 the corresponding compound of formula (I1).

The functional derivative of the acid used is preferably an acid chloride.

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

The subject of the invention is also a preparation process as defined before, characterised in that the compound of formula (II) is prepared by subjecting, in an organic solvent, a compound of formula (B^): (B1) 51431 in the form of a cis lactone, to the action of a compound of formula (Bg): ψ3 + P - CH - C-OE I o (b2) in which E keeps its previous meaning, to obtain the corresponding compound of formula (II): ROgC-CH » C in which the cyclopropane moiety is of 1R cis structure 10 in the form of a mixture of isomers E and Z, which is separated into each of the isomers.

In a preferred method of carrying out the invention, the solvent used is selected from the group constituted by diethyl ether, dimethyl sulphoxide, dimethyl formamide, tetrahydrofuran, dimethoxyethane, the alkanols, the monomethyl ether of diethyleneglycol and the diethyl ether of diethyleneglycol.

The compound of formula (Bg) is prepared hy the 5 action of a compound of formula: Ο Θ P-CH2-C02E, Hal Hal representing a halide anion, on a strong base. As strong base there may be used, for example, a hydride, an amide· or an alkaline alcoholate or an alkyllithium derivative.

The subject of the invention is also a preparation 10 process as defined before, characterised in that the compound of formula (II) is prepared by reacting a compound of formula (IV): Hi C02alk (IV) in which the cyclopropane moiety is of 1R cis structure and 15 in which Hal represents a halogen atom and alk represents an alkyl radical containing from 1 to 20 carbon atoms, firstly with an alkaline agent capable of removing the halogen atoms then, secondly, - either with an agent capable of intrnducj ng the carboxylic 2o group to obtain the compound of formula (V): (V) in. which the cyclopropane moiety is of 1R cis structure, which is subjected to the action of an esterification agent to obtain a compound of formula (VI): in which the cyclopropane moiety is of 1R cis structure and in which B keeps the same meaning as before, - or with a derivative of formula: Hal-CO2-B in which Hal represents a halogen atom and B keeps its previous manning, to obtain directly the compound of formula (VI): (VI) in which the cyclopropane moiety is of 1R cis structure, then the compound of formula (VI) is subjected to the action of a mild hydrogenation agent to obtain the compound of formula (VII): in which the cyclopropane moiety is of IR cis structure and in which the double bond has the geometry Z, which is subjected to the action of an acid hydrolysis agent capable of cleaving selectively the ester function on the carbon at position 1 of the cyclopropane, to obtain the corresponding compound of formula (II).

In a preferred method of carrying out the process above, - Hal represents a bromine or chlorine atom, - alk represents a tert-butyl or benzyl radical, - the alkaline agent capable of removing the vinyl halogens is butyllithium, - the agent capable of introducing the carboxylic group is carbon dioxide, - the mild hydrogenation agent is hydrogen in the presence of a catalyst such as palladium in the presence of traces of quinoline, and - the acid hydrolysis agent capable of cleaving selectively the ester function COgalc is paratoluene sulphonic acid.

The process also comprises a modification which is obvious to the chemist in which the compound of formula (V) is subjected firstly to the action of a mild hydrogenation agent then secondly to the action of a reducing agent.

. The subject of the invention is, therefore, also a modification of the process as defined before, characterised in that firstly the compound of formula (V) is subjected to the action of a mild hydrogenation agent to obtain the compound of formula (VIII): alk (VIII) in which the cyclopropane moiety is of 1R cis structure and in which the double bond has the geometry Z, which is subjected to the action of an esterification agent to obtain the corresponding compound of formula (VII): BOgC-CH-CH CO2alk (VII) in which the cyclopropane moiety is of 1R cis structure and in which R keeps its previous meaning, then the synthesis is carried out as described before.

The process above comprises a second obvious modification, in which the order of certain stages is modified.

The subject of the invention is, therefore, also a process as defined before, characterised in that a compound of formula (VI): CO2alk (VI) in which the cyclopropane moiety is of 1R cis structure and in which S and alk are defined as before, is subjected to the action of an acid hydrolysis agent capable of cleaving selectively the ester function at position 1 of the cyclopropane, to obtain the compound of formula (IX): in which S is defined as before, which - either is subjected, if it .is in the form of a functional derivative, to the action of an alcohol of formula (III): A'-OH (HI) in which A1 keeps the same meaning as before, to obtain the compound of formula (X): (X) in which the cyclopropane moiety is of 1R cis structure and in which B and A* keep the same meaning as before, which is subjected to the action of a mild hydrogenation agent, to obtain the compound of formula (I'), - or is subjected firstly to the action of a mild hydrogenation agent, to obtain the compound of formula (II): Η H HOgC—C=C (II) in which B is defined as before, in vidch the cyclopropane moiety is of 1R cis structure and the double bond has the geometry Z then, if it is in the form of a functional derivative, to the action of an alcohol (III), to obtain the compound of formula (I').

The preferred conditions for carrying out the process above are identical to those which have been defined before for similar operations.

The subject of the invention is-also a process for 514 51 preparing the compounds of formula (I1), characterised in that a compound of formula (ΣΙ): in which the double bond has the geometry Z, is subjected to the action of an esterification agent to obtain the corresponding compound of formula (I*).

In a preferred method of carrying out the process above the esterification is carried out with a functional derivative of an alcohol, namely a derivative of the 11,111 diisopropylurea of formula: Ϊ The subject of the invention is also a process as defined before, characterised in that the product of formula (XI) is prepared by subjecting an acid of formula (V) 514 in which the cyclopropane moiety is of 1R cis structure and in which alk represents an alkyl radical containing from 1 to 8 carbon atoms, to the action of 2,2£-trichloroethanol to obtain the compound of formula (XII): CO 2CH2CC1^ (XII) in which the cyclopropane moiety is of 1R cis structure, which is subjected to the action of an acid hydrolysis agent to obtain the compound of formula (XIII): CO^ (XIII) in which the cyclopropane moiety is of IR cis structure, which is subjected to the action of an alcohol of formula (III) A'-OH (IH) in which A' keeps the same meaning as before, to obtain the compound of formula (XIV): zCaC C02-A' co2ch2cci5 (XIV) in which the cyclopropane moiety is of 1R cis structure, which is subjected to the action of an agent for cleaving the ester function borne by the acetylenic carbon, to obtain the compound of formula (XV): in which the cyclopropane moiety is of 1R cis structure which is subjected to the action of a mild hydrogenation agent to obtain the compound of formula (XI).

In a preferred method for carrying out the process of the invention above, - alk in formula (V) represents a tert-butyl or benzyl radical; - the acid hydrolysis agent is paratoluene sulphonic acid; - the esterification of the compound (XIII) takes place by reacting the compound (XIII) with the alcohol (HI), in the presence of dicyclohexylcarbodiimide or of disopropyl carbodiimide; - the cleavage of the ester (XIV) takes place using a metal powder, for example zinc powder, in acid medium; and - the mild hydrogenation agent is hydrogen in the presence of a catalyst such as palladium, in the presence of traces of quinoline.

The process above comprises an obvious modification according to which the stages of hydrogenation and esterification are reversed.

The subject of the Invention is, thus, also a process as defined before, characterised in that a compound of in which the cyclopropane moiety is of 1R cis structure and in which A' is defined as before, is subjected to the action of an esterification agent, to obtain the compound in which the cyclopropane moiety is of 1R cis structure and in which K and A' are defined as before, which is subjected to the action of a mild hydrogenation agent, to obtain the compound of formula- (I1)· The preferred conditions for carrying out the process above are identical to those which have been defined before for similar operations.

For the case in which it is desired to prepare a compound of formula (I*)» in which B represents an alkyl radical substituted by one or more hydroxy radicals, there is prepared firstly, according to any one of the processes above, a compound, of formula (I'), in which E represents an alkyl radical substituted by one or more hydroxy radicals- protected, for example, by a dioxolanyl or tetrahydropyranyl group, then the said compound is hydrolysed by means of an acid hydrolysis agent.

The acid hydrolysis agent used in the process above can be, for example, hydrochloric acid or paratoluene sulphonic acid.

The majority of the processes which have just been described above lead directly to coapounds in which the double bond has the geometry Z. It is of course these processes which are the most suitable for the preparation of the compounds of formula (Is) in which the double bond has the geometry Z.

Excellent yields are obtained as is shown clearly 1$ by the experimental part set out hereinafter.

Compounds (ϋ) and (VI), as well as compounds (IX) and (X), obtained whilst carrying out the process of the invention are new chemical products. The subject of the invention is, therefore, also these products, as new chemical products, and more particularly as intermediate products necessary for the preparation of the compounds of formula (I') as defined before.

Example 1: (S) g-cyano 5-phenoxy benzyl (IR cis) 2,2-dimethyl ?C(Z) 3-(2,2,2-trifluoroethoxy) 3-oxo 1-propenyl] cyclopropane carboxylate. 1.3 g of (IS cis) 2,2-diaethyl 3t(Z) 3-oxo 3-(2,2,25 -trifluoroethoxy) 1-propenyl] cyclopropane carboxylic acid, 0.1 cm^ of pyridine and 15 cm^ of methylene chloride are mixed under agitation then 1.05 g of dicyclohexylcarbodiimide are added. 1.35 g of (S)e-hydroxy 3-phenoxy benzene acetonitrile in solution in 5 cm^ of methylene chloride are then added. The whole is agitated for 5 hours at ambient temperatryje and the insoluble matter is filtered off and rinsed with methylene chloride. 2N hydrochloric acid is added to the filtrate. This is decanted, washed with water, dried and brought to dryness. The oil obtained is purified by chromatography on silica (eluant: cyclohexane / ethyl acetate, 95:5). 1.33 g of the product sought are thus obtained. aD * +42° ί 2° (c « 0.7 benzene) HMR CDC1 ?! p- .p.m. of the20 1.26 and •1.28 H 1.97 - 2.11 H of the 3.1 to 3.4 H of the 6.5 to 6.9 H of the 5.9 - 5.93 H of the 25 6.3 H of the 4.3 to 4.7 H of the In example 1 the acid used is prepared as follows: Preparation I : (IB cis) 2,2-dimethyl 3((Z) 3-(2,2,2-trifluoroethoxy) 3~oxo l-propenyl3 cyclopropane carboxylic acid.

Stage A: 1, l·- di methjlethyl X.1B ci^J^-dj^tl^-^-^xh^roxy5 i"£x£ lyjiropjnyl^ cyclopro^ane^carboxylatej. g of 1,1-dimethylethyl (IB cis) 2,2-dimethyl 3-(2,2-dibromovinyl) cyclopropane carboxylate are introduced into 175 cm^ of anhyri roiw tetrahydrofuran. 60 cm^ of a 20% solution of butyl lithium in cyclohexane are then added at -65°C. The whole is agitated for 1 hour at -60°G then a current of carbon dioxide is bubbled in for an hour and a half and the reaction mixture is poured into iced water to which has been added N sodium hydroxide. The whole is washed with ether. The alkaline aqueous -phase is acidified to pH 4 and extracted with ether. The organic phases are dried and brought to dryness under reduced pressure. A product is thus obtained which is recrystallised from petroleum ether (B.Pt. 60-80°C). 8.3 g .of the product sought, melting at 144°C, are then obtained.

HUB GDC1 P · J) ·Φ· 1.22 and 1.37 : protons of the methyls at 2 of the cyclopropane, 1.78 : proton at 1 and 3 of the cyclopropane, 1.47 ·· protons of the tertbutyl, 8.25 : proton of the group -C-OH · Stage B: 1., 1-dimethylethyl _£1B ei^^Bj.B-dimethyl-^.-C^Xpxo23£(2,2,2~£r£f^u£r£eth£:!2)_l^£0£yT^l]_c2elp£r£pame £arb£xylate g oi the product prepared in Stage A and 3·5 g of dicyclohexylcarbodiimide are introduced into a solution containing 20 cm^ of methylene chloride and 1 cm^ of pyridine. The reaction mixture is maintained under agitation for 1 hour. 2.15 g of trifluoroethanol and 5 cm^ of methylene chloride are then added. The whole is maintained under agitation at 20°C for 16 hours. It is filtered and rinsed with methylene chloride. The filtrate is brought to dryness. It is taken up with sulphuric ether, washed with N hydrochloric acid then with water and dried, it is concentrated and 5 g are isolated of a product which is chromatographed on silica (eluant: benzene / ethyl acetate, 95s5)· 3-5 g of product sought are thus obtained.

NMR CDCl^ : p.p.m. 1.2 and 1.37 1-77 1.43 4.3 to 4.7 H of the methyls at 2, H of the carbons at 1 and 3 of the cyclopropane, Ξ of the methyls of the 1,1-dimethylethyl radical, H of the trifluoroethoxy radical.

Stage C: £1R ^is^j^dimethyl. l(l-oxo.-T-£2j.2j.2-trif luo^o^. £thoxy2l^pro£ynyl]_cjcl,o£ropane _ca£boxylic_acid.

A mixture containing 3.3 g of product prepared in the previous stage, 3θ cm^ of toluene and 100 mg of paratoluene sulphonic acid is taken to reflux and maintained at reflux until the release of gas has finished. It is cooled, washed with water, dried and brought to dryness. 2.6 g are thus obtained of the product sought which is used as it is in the following stage.

Stage D: _£1B £Ϊ£)_2Α2-dimethyl ^.(£Zj_-^-oxo_-j7£2j_2j.2-tri5 f luo£O£thoxy2 l-Jiropepyl] cycloprojoane_carhoxylic. acicL· 500 mg of 10% palladium hydroxide on barium sulphate and 5 cm^ of ethyl acetate are placed in a round flask connected to a hydrogen apparatus. 2 g of the product x prepared in the previous stage, 45 c® of ethyl acetate and 0.5 cm^ of quinoline are added.. Hydrogenation is carried out until absorption has finished. The product obtained is filtered. The filtrate is washed with H hydrochloric acid then with water and brought to dryness. 2 g are obtained of a product which is chromatographed on silica (eluant: cyclohexane / ethyl acetate / acetic acid, 70:30:1)· 1-5 S of the product sought are thus obtained.

NMR Spectrum CDC1, p.p.m. 1.3 and 1.32 H of the 1.92 - 2.06 H of the 3.07 to 3-38 H of the 6.6 to 6.9 H of the 5-9 - 6.0 Ξ of the 4.3 to 4.7 Ξ of the 1.92 - 2.06 H of the carbon at 1 of the cyclopropane, H of the carbon at 3 of the cyclopropane, H of the carbon at 1 of the propenyl radical Ξ of the carbon at 2 of the propenyl radical H of the trifluoroethoxy radical.

Example 2; (IS) 2-dimethyl-4-oxo-3-(2-propenyl) 2-cyclopenten -1-yl (IR cis) 2,2-dimethyl-3-i(Z)-3-oxo-3-(2,2,2-trifluoroethoxy) l-propenyl3 cyclopropane carhoxylate. 1.9 g of (IB ois) 2,2-dimethyl 3((Z) 3-oxo-3-(2,2,2-trifluoroethoxy) 1-propenyl] cyclopropane carboxylic acid, 12 cm3 of methylene chloride and 100 ng of dimethylamino pyridine are aixed. 1.4 g of dieyclohexylcarbodiimide are then introduced then 1.1 g of (S) 3-(2-propenyl) 1-hydroxy 2-methyl 4-oxo cyolopent-2-ene and 5 cm^ of methylene chloride. The whole is maintained under agitation at ambient temperature for 2 hours. The insoluble matter formed is eliminated by filtration. The filtrate is washed with 0.5 B hydrochloric acid', then with water, it is dried and it is brought to dryness. $ g are thus obtained of a product which is chromatographed on silica (eluant: benzene / ethyl acetate, 95:5)· 2.2 g of the product sought are thus obtained.

D » +38° - 2.5° (c 0.5% benzene) NHB Spectrum CDCl^ p.p.m. 1.29 and 1.32 1.97 - 2.11 3.05 to 3-37 6.7 to *7 5-9 J 6.1 ) 4.3 to 4.71 5-7 . 2 4.8 to 5.25 H of the methyls at 2 of the cyclopropane, H at 1 of the cyclopropane, H at 3 of the cyclopropane, H of the carbon at 1 of the propenyl radical, H of the carbon at 2 of the propenyl radical, H of the trifluoroethoxy radical, H of the cyclopentene at a of the C02, H of the methyl borne by the cyclopentene, H of the 3 of the propenyl borne by the cyclopentene.

Example 3: (IS) g-cyano-5-phenoxy benzyl (IB cis) 2,2-dimethyl 5[(Z)-3-oxo 3-(phenylmethoxy) 1-propenyl] cyclopropane carboxyiate.

Stage A; £lB £Ϊ3.)_2Α2-άίιηβί:Η7ΐ ^,-£(Z)_5xoxox3z(£hen2lmethox2)_ 5 l-Jiropenjli cyclopropane_carboxyli£ acid_chloride.

A mixture containing 1.6 g of (IB cis) 2,2-dimethyl 3ί(Z) 3-oxo 3-(phenylmethoxy) 1-propenyl] cyclopropane carboxylic acid, 10 cm^ of isoprene and 1 cra^ of thionyl chloride is agitated for 5 hours under a current of nitrogen then concentrated and 2 g are thus obtained of a product « which is used as it is in the following stage.

Stage B: (,lS)o[-cyano.-2,-£henox2 benzxL_(lB_cis.X 2 dim ethyls, s5yCXz2-^-£X£ X"XpbenylmethoxyX l-^ropenyl] cy£lopro£ane_ carboxyiate.. 1 g of the product prepared in Stage A is introduced into a solution containing 700 mg of (S) α-hydroxy 3-pbenoxy benzene acetonitrile, 20 cm^ of benzene and 0.6 cm^ of pyridine. The reaction mixture is maintained under agitation for 16 hours, at ambient temperature, and poured on to a mixture of iced water and N hydrochloric acid. The suspension obtained is agitated and extracted with benzene.

The benzene extracts are washed with water, dried, filtered and brought to dryness. 1.5 g are obtained of a product which is chromatographed on silica (eluant : cyclohexane / ethyl acetate, 8:2). 861 mg of the product sought, melting at 83°C, are thus obtained. aD > +69° ~ 5° (c » 0.2% benzene). NMR Spectrum CDCl^ p.p.m. 1.25 6.33 H of the methyls at 2 of the cyclopropane, H of the carbon bearing the ON group.

Preparation II : (IR cis) 2.2-dimethyl-3-[(Z)-3~oxo-3-(phenyl methoxy)-l-propenyl3 cyclopropane carboxylic acid.

Stage kt i,l-dimethylethyl. £1R ci^)_2j_2-di.m£thyl 2.LQZ2 2-£arbox2 pthenylJ-Cyclopropane carboxylate. g of 1,1-dimethylethyl (IR cis) 2,2-dimethyl 3(210 -carboxy ethynyl] cyclopropane carboxylate in 40 cm^ of ethyl acetate are hydrogenated in the presence of 0.38 g of 10% palladium hydroxide on barium sulphate and 0.4 cm^ of quinoline. The whole is filtered, the filtrate is washed with 0.5 N hydrochloric acid, then with water until neutral, flried and concentrated to dryness under reduced pressure and 2 g of the product sought, melting at 94°C are obtained.

Stage B: .lj^-dimethylethyl. £lR cis>)_2J.2£dimethyl-2.-X.(Z)^-oxo^Z.ijEbenj^methoxy^’i-E^SPZ1! cyc.lopropan.e_carboxylate.j. 2.4 g of the product prepared in Stage A are introduced into 20 cm^ of ethyl acetate. 2.34 g of 0-benzyl N,N-diisopropyl isourea (described by ESCHIMBT et al Liebig Ann. Chem. 1965 685 161), are then added. The whole is agitated for 16 hours at ambient temperature and filtered and the filtrate is concentrated under reduced pressure. 4.3 g are obtained of a yellow oil which is chromatographed on silica (eluant: benzene / cyclohexane, 7:3)· 2 g of the · product sought are thus obtained.

NMB Spectrum CDCl^ p.p.m 1.22 and 1.28 H of the 1.77 - 1.91 Ξ of the 2.98 to 3.3 H of the 6-5 to 6.8 H of .the 5-8 - 6 H of the 1.4-3 H of the 5.1 H of the Stage C: (lH_cis). 2, ,2-dimet .l-joropenyl] cy£lopro£ane_cjirbpxyli£ acicL.

A mixture containing 2 g of the product prepared in X the previous stage, 30 cm of toluene and 100 mg of paratoluene sulphonic acid is taken to 90°0. It is maintained under agitation for about 2 hours. It is brought to dryness and 2 g are obtained of a product which is chromatographed on silica (eluant: cyclohexane / ethyl acetate / acetic acid, 60:40:1). 1.4· g of the product sought are thus obtained.

HMB Spect-rum CDCl^ p.p.m. 1.25 and 1.3 H of the 1.84- - 1.98 H of the 3.14 to 3.43 H of the 6.4 to 6.77 H of the methyls at 2 of the cyclopropane, carbon at 1 of the cyclopropane, carbon at 3 of the cyclopropane, carbon at 1 of the propenyl radical, · 5-98 H of the carbon at 2 of the propenyl radical.

Example 4: (lS)-2-methyl-4-oxo-5(2-propenyi) 2-cyclonenten-l-yl (IB cis) 2,2-dimethyl 3~C(Z) 3-oxo-3-(phenyl-methoxy)-l-propenyl] cyclopropane carboxylate. g of (IR cis) 2,2-dimethyl 3C(Z) 3-oxo-3(phenylmethoxy) l-propenyll cyclopropane carboxylic acid chloride is introduced into a mixture of 450 mg of (S) 3"(2-propenyl) 1-hydroxy 2-methyl 4-oxo cyclopent-2-en-l-yl, 20 cm^ of benzene and 0.6 cm^ of pyridine. The whole is maintained under agitation for 16 hours and the reaction mixture is poured on to a mixture of iced water and N hydrochloric acid. The whole is extracted with benzene and the benzene phases are combined, washed with water, dried and brought to dryness. 1.5 g are obtained of a product which is chromatographed on silica (eluent: cyclohexane / ethyl acetate, 8:2). 500 mg of the product sought are thus obtained, benzene) "D * +37° * 2.5 (c - 0.55 15 NMR Spectrum CDC1, p « p · Hl 1.27 and 1.31 H of 1.87 - 2 H of 3.12 to 3.45 H of 5-8 to 6.8 H at 20 5-2 H of radic 5-6 to 5-7 H of 2 H of 4.8 to 5.2 H of . Example 5: (S) g cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3C(Z)-3-oxo-3-phenoxy-1-propenyl] cyclopropane carboxylate.

Work being carried out as in Example 1, starting with 1.5 g of(lR cis) 2,2-dinethyl-3((Z) 3-oxo-3-phenoxy-1-propenyl] cyclopropane carboxylic acid and 1.45 E of (S) a-hydroxy 3-phenoxy benzene acetonitrile, 1.8 g of the product sought are obtained. aD = +54° - 2.5° (c = 0.% in benzene) MMB Spectrum OJCl^ p.p.m. 1.25 H at 2 of the cyclopropane, 1.97-2.12 H at 1 of the cyclopropane, 3.25 to 3·6 H at 3 of the cyclopropane, 6.6 to ?' Ξ at 1 of the propenyl radical, 6.1 - 6.3 H at 2 of the propenyl radical, 6.9 to 7.7 aromatic H*s of the 3-phenoxy phenyl radical. Preparation III: (IE cis) 2.2-dimethy1-3((2) 3-oxo 3-phenoxy— -l-propenyl3 cyclopropane carboxylic acid.

Stage. A: 1,1.-dimethylethyl £1E £is)_2x2-di^£tl^l-2-£3zoi£oZ 232phenoxy2lxPZ°25L7l.^_c2ci0£r2P5?1£ ^artoxylate. g of 1,1-dimethylethyl (lRcis) 2,2-dimethyl 3-(21,2'-dibromovinyl) cyclopropane oarboxylate are dissolved in 25Ο cn^ of tetrahydrofuran. 48 cm^ of a 20% solution of butylldthium in cyclohexane are then introduced under agitation at -65°C. The agitation is maintained for one hour at ~65°C and 9-6 cm^ of phenyl chloroformate are introduced. The whole is maintained again under agitation at -65°C, for one hour, and allowed to return to ambient temperature, whilst the agitation is maintained. It is poured on to a saturated aqueous solution of monosodium phosphate, extracted with ether, washed with water and dried and 24.6 g are obtained of an oil which is purified by chromatography on silica-(eluant: cyclohexane / ethyl acetate, 9:1). 14.4 g of the product sought are thus isolated.

NMR Spectrum GDOl^ p.p.m. 1.23 and 1.42 1.82 1.5 to 7.6 H of the methyls at 2 of the cyclopropane, H at 1 and 3 of the cyclopropane, H of the dimethyl ethyl radical, aromatic H's.

Stage B: 1,1,-dimethylethyl £1B c.is)l_2x2-dim^thyl-^-X(Z)_ ^-oxq-^-jDhenoxy-l-jqrop^nylj. eyelppjropane_c arboxylate.

In the presence of 800 mg of palladium hydroxide on barium sulphate, 0.8 cm^ of quinoline and 20 cm^ of ethyl acetate, 4 g of the product prepared in Stage A in solution in 60 cm^. of ethyl acetate are hydrogenated and filtered and 200 cm^ of a 2tf solution of hydrochloric acid are added. The whole is decanted, washed with water and dried. 4.1 g are obtained of an oil which is purified on silica (eluant: cyclohexane / ethyl acetate, 95:5)· 3·35 B °f the product sought are obtained.

NMR Spectrum CDCl^ p.p.m. 1.23 and 1.3 H at 2 of the cyclopropane, 1.83 - 1.97 H at 1 of the cyclopropane, 3 to 5.53 H at 3 of the cyclopropane, 1.44 H of the methylethyl radical, 6.7 to 7 H at 1 of the propenyl radical, 6.03 - 6.21 H at 2 of the propenyl radical, 7 to 7.5 aromatic H's.

Stage C:· £1H £is)_2j2xdim£tl^l-;5-£(Z)^-oxo^2?he]io2y_ .l-jaMpenyl]. cyclopr.o^ane^arboxylic. SLCidx A mixture of 3.3 g of the product prepared in the previous Stage, 35 cm^ of toluene and 100 mg of monohydrated paratoluene sulphonic acid is taken to reflux. The refluxing is stopped as soon as the release of gas has finished.

The whole is brought to dryness under reduced pressure and 3.4 g are obtained of a product which is chromatographed on silica (eluant: cyclohexane / ethyl acetate / acetic acid, 70:30:1). 2.4 g of the product sought are obtained, melting at 57°C· NMB Spectrum ODCl^ p.p.m. 1.25 to 1.33 H of the methyls at 2 of the cyclopropane, 1.9 - 2.04 H at 1 of the cyclopropane, 3.2 to 3.5 H at 3 of the cyclopropane, 6.6 to 6.9 H at 1 of the propenyl, 6.0 - 6.2 H at 2 of the propenyl.

Example 6: (IS) 2-methyl 4-oxo-3-(2-propenyl) 2-cyclopenten-1-yl (IB cis) 2,2-dimethyl-3C(Z)-3-oxo-3-phenoxy-l-propenyl] cyclopropane carboxylate.

Work being carried out as in Example 2, starting with 1.5 g of (IB cis) 2,2-dimethyl-3[(Z)-3-oxo 3-phenoxy-l-propenyll cyclopropane carboxylic acid and 1 g of (S) 3-(2-propenyl) 1-hydroxy 2-methyl 4-oxo cyclopent-2-en-l-yl, 1.6 g of the product sought are obtained, a +66° - 2.5 (c = 0.5% benzene).

NMB Spectrum CBClj p.p.m. 5143* 1.26 and 1.33 H at 2 of the cyclopropane, 1.95 - 2.09 H at 1 of the cyclopropane, 5-7 Ξ of the cyclopentene at a of the C02, 4.8 to 5.2 H at 3 of the propenyl borne by the cyolopentene, 2 Ξ of the methyl borne by the cyclopentene, 6.1 to 6.7 H of the propenyl borne by the cyclopropane 7 to 7.7 aromatic H's.

•Rvample 7: (RS) α-cyano 3-phenoxy benzyl (IR cis) 2,210 -dimethyl-3[(Z)-5-oxo-5-methoxy methoxy 1-propenylj eyelopropane c arboxylate.

Stage A: (RS)_a-c2ano_3^pheno/y_b£nzy_l £lR £is)_2x2xdimethyl"3"Q-ox£".^iSe£b.2.xz; methoxy lyRropynyl). cyclopr°£ane_ £arboxylate.· A solution of 5 g of (RS) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-(3"bydroxy 3-oxo 1-propynyl) cyclopropane carboxyate in 3θ cm^ of anhydrous dimethyl formamide is cooled to +10°C, 300 mg of.61% sodium hydride in oil are added in portions then, over -15 minutes, 2.5 car 20 of chloromethyl ether solution prepared as below. The whole is agitated for 2 hours, poured on to an aqueous solution of monosodium phosphate and extracted with ethyl acetate, washed with water, dried and concentrated to dryness. The residue is chromatographed on silica and eluted with a mixture: cyclohexane / ethyl acetate (75:25) and 2 g of expected product are recovered.

SIR Spectrum CDClj p.p.m. 51 1.23 - 1.27 and 1.35 - 1.45 protons of the methyls at 2 of the cyclopropane, 1.95 protons at 1 and 3 of the cyclopropane, .28 proton of the methylene of the methoxy methoxyl, 3.5 proton Of the methyl of the methoxy methoxyl, 6.42 and 6.47 proton borne by the same carbon as CN, 6.92 to 7·5θ aromatic protons, Preparation of the chloromethyl ether solution. 4.5 cm^ of methylal and 0.52 cm^ of methanol are mixed then 3.53 cm^ of acetyl chloride are added slowly.

The whole is agitated for 36 hours at ambient temperature to obtain the expected solution.

Stage B: £HS)_a-cyanoJsphenoxy_hen.syl £1E c.i£)_2_i2-dimethyl£3_[(Z)^3-oxo-32.m£thoxy_m£thoxy_l£proOenyl]_c2c].ouropane carboxyl a t£. 2.2 g of product obtained as above in 50 cm^ of ethyl acetate are hydrogenated in the presence of 450 mg of 10% palladium hydroxide on barium sulphate in 30 cm^ of ethyl acetate and 0.5 om^ of quinoline. The whole is filtered And the filtrate is washed .with N hydrochloric acid and with water, dried and brought to dryness. The residue is chromatographed on silica and eluted with a mixture: cyclohexane / ethyl acetate (8:2) and 1.2 g of expected product are recovered. aD » +41° ± 3 (c = 0.3% CHClj) NMH CDClz p.p.m. 1.27 - 1.28 and 1.33 - 1·35 protons of the methyls at 2 of . the cyclopropane, 1.93 ~ 2.1 proton at 1 of the cyclopropane, 3.17 to 3-5 proton at 3 of the cyclopropane, 6.47 to 6.82 ethylenic proton at 1, .85 - 6.0 and 5·88 - 6.1 ethylenic proton at 2, .27 and 5.3 proton of the CH2 of the methoxy, 3.47 and 3·5 protons of the methyl of the methoxy, 6.4 home by the same carbon as CN, 6.92 to 7-67 aromatic protons.

The (ES) α-cyano 3-phenoxy benzyl (IE cis) 2,2-dimethyl 3-C-3-hydroxy 3~oxo 1-propynyl] cyclopropane carhoxylate « used at the beginning of the Example can be prepared in a maimer similar to that for the (S) ester described further on, using the corresponding (ES) alcohol.

Example 8; (S) «-cyano 3-Phenoxy benzyl (IB cis) 2.2-dimethyl-3-i(Z)-3-oxo.3-cyano methoxy 1-propenylJ cyclopropane carhoxylate.

Stage A: ^,^)_a^cyanp__3^phenoxy_benzyl £1B £i£)_2x2-dimethyl^3" [^yoxo 2,-cyano. methoxy lyEropynyl]. cyc.lopro££me__carboxylat.ex x Work is carried out as in Example -7 using 2 cur of chloro-acetonitrile; after extraction with ether and elution with a mixture: cyclohexane / ethyl acetate (9:1) 2.69 g of expected product are obtained.

Stage Β: Ai^—^S^dimethyly3" CLQ".2r2.x2. i"oyano methoxy 1-propenylJ cyclop_ro£ane_ £arboxylate.

Work being carried out as in Example 7, starting with 2.69 g of the product obtained atove, 2.02 g of expected 451 product are obtained after elution with a mixture: cyclohexane / ethyl acetate(9:l).

Stage C: £S2 a-cyano ^.-phenoxy benzyl_(lR_cis2. 2,2-dimethyl2,3,2(£.Z2-2,-£xo ji-cyano methoxy l-propenyl], eycloprppane_ carboxyl.ate. 1.4 g of the product above are chromatographed on silica and eluted with methylene chloride and 0.41 g of expected product is obtained. aD = +55° ί 1.5 (c - 1% CHC13) Example 9:(S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-ethoxyethoxy l-propenyl] cyclopropane carboxylate Stage A: α-cyanp ^-phenoxy benzyl_(l.B_cpsT. 2,,2-dimephyl2 -^-[_2.-o,xp-^-£thoxyethoxy_lppropynyl]_cyc^oprppane carbpxylat^. g of (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl 3-(3"bydroxy 3~oxo 1-propynyl) cyclopropane carboxylate, 20 cm^ z of methylene chloride and 0.7 cur of ethoxy ethanol are cooled to 0 to +5°C. 1.1 g of dicyclohexylcarbodiimide, cm^ of methylene chloride and 15 ng of dimethylaminopyridine are added. The whole is agitated for 1 hour at +5°C and for 2 hours at ambient temperature. It- is filtered, the filtrate is concentrated to dryness and the residue is chromatographed on silica and eluted with a mixture: cyclohexane / ethyl acetate (75:25) and 1.3 g of expected product are obtained.

NMR CDCl^ p.p.m. 1.22 - 1.32 protons of the methyls at 2 of the cyclopropane, 1.93 protons at 1 and 3 of the cyclopropane, 4.17 to 4.38 protons at 1 of the COO-CHg-CHg0 3.55 to 3·73 protons at 2 of the C00-CH?-Gg3-0, 6.57 proton borne by the same carbon as CN, to 7·67 aromatic protons, 1.08 - 1.2 - 1.3 and. 1.52 (q) protons of the ethyl.

Stage B: £S}. a-cyan2-^-_£henoxj benzyl_(lR_cis2 ^«^-dimethyl 1(Ϊ.ζ2~5γ£χ£ l"i,ath£X2 ethoxy). i-£r2P£nll2 carboxylate..

Work being carried out as in Example 7» Stage B, starting with 1.3 g of the product obtained above, 1.0 g of expected product is obtained. aD - +37-5° * 2.5°(c - 0.% 0H015) Example 10; (S) tx-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-C(2)-3-oxo 3(3S)(1,1.1,trifluoromethyl ethoxy) l-propenyl3 cyclopropane oarboxylate.

Work is carried out as in Stage B of Example 7, using 2.6 g of (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl 3-(3"Oxo 3"&BS) 1,1,1-trifluoromethyl ethoxy) propynyl] cyclopropane oarboxylate. After elution with a mixture; cyclohexane / ethyl acetate (9:1), 2.1 g of expected product are obtained. cxg » +44° - 2 (e » 0.4% benzene).

Preparation of (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl 3[5-oxo 3-((RS) 1,1,1-trifluoromethylethoxy) propynyl3 cyclopropane oarboxylate.

Work is carried out as in Stage A of Example 9, using 4.6 g of 1,1,1-trifluoromethyl ethanol and 3.8 g of (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl 3-C3-OXO -hydroxy propynyl] cyclopropane carboxylate, to obtain, after elution with a mixture: cyclohexane / ethyl acetate (8:2), 2.6 g of expected product.

Example 11; (S) α-cyano 3-pbenoxy benzyl (IR cis) 2,2-dimethyl· 5 -5-E(Z)-5-oxo 5-(2,2-difluoroethoxy) propenyl] cyclopropane carboxylate.

Stage A: Tert-butyl-i.lRjsisj. 2,2-dimethylx5x.C^.-oxo ^.-£2X2-difluo r oethoxy) _pronynyl]_cyclojjropane carboxyl ate.

Work being carried out as in Stage A of Example 9, starting with 5 g °f tert-butyl (IE-cis) 2,2-dimetbyl-3-(3-hydroxy 3-°xo-l-propynyl] cyclopropane carboxylate and after elution with a mixture n-hexane / isopropyl ether (7:3), 5.25 g of IS chci5 -CsC- conj.

CaO ester asymmetric gem. dimethyl tert-butyl .Stage B: £1R £is.)_2j_2-dim£thyl-^.-C.3^P2°_32.(2,2-difluoro£thoxy)_ l.-£ropyn.yl2 cy£lop£0£ane_carboxyli£ acid.^ .2 g of the product obtained above end 5°° mg of paratoluene sulphonic acid in 40 cm^ of toluene are heated to reflux for 25 minutes. After cooling, 400 cm^ of ether are added, the whole is washed with water and the organic phase is dried and concentrated to dryness to obtain 4.1 g of expected product. expected product are obtained. 2232 cm-1 1725 cm1 1710 cm-1 (1395 cm-1 (1380 cm-1 1372 cm-1 514 51 Stage C: £S}_ a-cyano 2."£h£n£xy keS22^«.(i®_cisi 2,2-dimethyl· l-i2x2-difl.uoroethox2)_l2liro£ynyl]_cyclo£ropaQ£ £arboxylate.

Work being carried out as in Stage A of Example 9, starting with 4.1 g of the acid obtained above and 4.5 g of (S) α-cyano 3-phenoxy benzyl alcohol, 4.7 g of expected product are obtained after elution with a mixture: petroleum ether (B.Et. 40-70°C) / isopropyl ether (6:4).

IE CHC1, OH 3580 cm-1 gem.di Me (1392 cm'1 (1380 cm'1 -C3C- conj. 2235 cm-1 C»0 ester 1755 cm-1 conj. ester 1725 cm'1 aromatics. ( 1588 cm'1 ( 1488 cm'1 Stage D: £S2 α-cyano j^-jrtienoxy benzyl_(l.R_cis2 .2,2-dimethyl· z3;;C£Z}.-,2roxo ^-jk2x2ydifl,u£roe£h£xy)_pro£enyl]_cycjio£rppan£ carboxylate.. 4.7- g of product obtained above are hydrogenated in the same manner as in Stage B of Example 7· After elution with a mixture:n-hexane / isopropyl ether (7:3), 3-2 g of expected product are obtained. aD . +44° ± 2.5 (c » 0.5% CHClj) Example 12: (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-5-C(Z)-5-(2,2-dichloroethoxy) 1-propenyl] cyclopropane carboxylate. 51-451 Stage A: Tertybutyl_(lB_cis£ £,2-dimethyl23;iCXZ£"£-X2_i2ydichlpro ethoxy). l.-£ropenylX cy£lop£ooane_c£rbp^Late;.

Work is carried out as in Example 9 of Stage A, starting with 4.8 g of tert-butyl (IB cis) 2,2-dimethyl-3-[(Z) 35 -hydroxy 3-oxo 1-propenyl] cyclopropane carboxyiate and cm^ of 2,2-dichloroethanol. After elution with a mixture: cyclohexane / ethyl acetate (9:1), 5-6 g of expected product are obtained.

Stage Β: χΐΒ £i£)_2j2ydim£thyl-^-X(£)23T.(X,2-di£h].0£oethoxy). lyjjrnpenyl]. £ycloprp£ane_carboxyli£-acid^.

Work is carried out as in Stage B of Example 11, starting with 5·θ S of product above and 4.5 g of expected product are obtained.

Stage £: (S) J*ycyano^3>heno3^_benzy.l χΐΒ £i£)_2j.2ydimethyl15 y3yCXZX-X-X2j.2-di.chlor£ethox2)_l^pro£enyl]_c2Cl.o£r£pane £arb£xylat£.

Work is carried out as in Stage A of Example 9, starting with 5 S of the product obtained at B and 2.25 g of (S) α-cyano 3~phenoxy benzyl alcohol. After elution with mixtures: cyclohexane / ethyl acetate (8:3) then (9:1), 1.6 g of expected product are obtained. aD =, 4540 - 2° (c =, 1% in benzene).

The following Examples are prepared in a manner similar to that described in Stage A of Example 9, starting with: 1) (IB cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-(2,2-difluoroethoxy) 1-propenyl] cyclopropane carboxylic acid and the corresponding alcohol.

Example 13: (RS) a-cyano 6-phenoxy 2-pyridyl methyl (IS cis) 2,2-dimethyl-3-[(Z)-5-oxo 3-(2,2-difluoroethoxy) 1-propenyl] cyclopropane carboxylate. aD . +50.5° 1 2° (o . 0.8% CHClj) Example 14: (R) g-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-(2,2-difluoroetfaoxy) 1-propenyl] cyclopropane carboxylate, aD - +117.5° 1 3° (c - 0.6% CHClj) ' Example 15: C 5-propargyl-2,5-diox 1-propenvl] cyclopropane carboxylate. aD - +18° i 2° (c « 1% CHClj)' Example 16: (R) α-ethynyl 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-[(Z)-5~oxo 3-(2t2-difluoroethoxy) 1-propenyl] cyclopropane carboxylate. aD - +47° ± 1.5*(c - 1% CHClj) The (IR cis) 2,2-dimethyl-3-C'(Z)-3-oxo 3-(2,2-difluoroethoxy) 1-propenyl] cyclopropane carboxylic acid was prepared in a manner similar to that described in Preparation VI, starting with 2,2-difluoroethanol. 2) (IR ois) 2,2-dimethyl 3-C(Z)-3-oxo 3-(2-fluoro ethoxy) 1-propenyl] cyclopropane carboxylic acid and the corresponding alcohol.

Example 1?: (3-propargyl 2,5-dioxoimidazolidinyl) methyl (IR cis) 2,2-dimethyl-3-i(Z)-3-oxo 3-(2-fluoro ethoxy) l-propenyl]cTclopropane carboxylate. aD - +18° i 2° (c - 1% CHClj) Example 18: (RS) α-cyano (6-phenoxy 2-pyridyl) methyl (IR cis) 2,2-dimethyl-5-i(Z)-3-oxo 3-(2-fluoro-ethoxy)-l-propenyl]eyelopropane carboxylate. aD = +49.5° 2.5° (c =. 0.% CHClj) Example 19; (R) α-methyl 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-(2-fluoro-ethoxy)-l-propenyl3 cyclopropane oarboxylate. aD - +123° i 1.5°(o = 1% CHOip Example 20: α-ethynyl 3-phenoxy benzyl (1R cis) 2,2-dimethyl10 -3-C(Z)-3-oxo 3-(2-fluoro-ethoxy)-l'-propenyl] cyclopropane oarboxylate. ccD . +47° i 1.5° (c = 1% CHClj) The (IR cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-(2-fluoro ethoxy) 1-propenyl] cyclopropane carboxylic acid was prepared in a manner similar to that described in Preparation VI starting with 2-fluoroethanol. 3) (IR cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-(2-(1,1,1,3,3,3-hexafluoro) propoxy) 1-propenyl] cyclopropane carboxylic acid (Preparation VI) and the corresponding alcohol.

Example 2.1: (R) α-ethynyl 3-phenoxy benzyl (IR cis) 2,2-dimetbyl-3-((Z)-3-oxo 3-(2-(1,1,1,3,3,3-hexafluoro) propoxy) 1-propenyl] cyclopropane oarboxylate. aD - +31.5° - 1-5° (c = 1% CHClj) Example 22: (R) α-methyl 3-phenoxy benzyl (IR cis) 2,225 -dimethyl-3-C(Z)-3~oxo 3-(2-(1,1,1,3,3,3-hexafluoro) propoxy) 1-propenyl] cyclopropane oarboxylate. aD = +97° i 2°(c = 1% CHC15) • 60 sl4Si Example 2?: (S) α-cyano 3-phenoxy benzyl (IR cis) 2.2- dlmethyl-3-C ( Z) -3-oxo 3-(2-(1,1,1,3,3,3-hexafluoro) propoxy) l-propenyl] cyclopropane carboxylate. aD > +23.5° " 2° (c 0.5% benzene) Example 24: 3,4,5,e-tetrahydrophthalimido methyl (IR cis) 2.2- dimethyl-3-((Z)-3-oxo 3-(2-(1,1,1,3,3,3-hexafluoro) propoxy) l-propenyl] cyclopropane carboxylate.

D « -30° ί l°(c - 1% CHClj) Example 25: (RS) cyano β-phenoxy 2-pyridyl methyl (IR cis) 2.2- dimethyl-3-[(Z)-5-oso 3-(2-(1,L, 1,3,3,3-hexafluoro) propoxy) l-propenyl3* cyclopropane carboxylate. aD . +33-5° - 2.5° (c - 0.2% OHClj) 4) (IR cis) 2,2-dimethyl-3"C(Z)-3~oxo 3-(2,2,2-trifluoro ethoxy) l-propenyl] cyclopropane carboxylic acid (Preparation I) and the corresponding alcohol.

Example 26: (3-propargyl 2,5-dioxoimidazolidinyl) methyl (IR cis) 2,2-dimethyl-3-[(Z)-5-oxo 3-(2,2,2-trifluoro ethoxy) l-propenyl] cyclopropane carboxylate. a^ » -4° .-1° (c - 1% benzene).

Example 2?: (R) α-methyl 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-(2,2,2-trifluoro ethoxy) l-propenyl] cyclopropane carboxylate. aD - +108.5° - 2° (c » 1% CHClj) Example 28: 3,4,5,6-tetrahydrophthalimido methyl (IR cis) 2.2- dimethyl-3-C(Z)-3-oxo 3-(2,2,2-trifluoro ethoxy) l-propenyl] cyclopropane carboxylate. aD > +2.5° - 2°(c - 0.5% CHClj)’ Example 29: (Η) α-ethynyl 3-phenoxy benzyl (IR cis) 2.2- dimethyl-3-C(2)-3~oxo 3-(2,2,2-trifluoro ethoxy) 1-propenyl] cyclopropane carhoxylate. aD = +42° ± 1.5°(c = 1% CEC13) Example 30: (RS) α-cyano 6-phenoxy 2-pyridyl methyl (IS cis) 2.2- dimethyl-3-i(Z)-3-oxo 3~(2,2,2-trifluoro ethoxy) 1-propenyl] cyclopropane carhoxylate. aD = +46.5° - 2° (c = 0.7% CHOlj) ) (S) α-cyano 3~phenoxy benzyl (IS cis) 2,2-dimethyl-310 -C(Z)-3-hydroxy-3-oxo 1-propenyl] cyclopropane carhoxylate (Preparation VII) and the corresponding alcohol.

Example 31: (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-5-C(Z)-3-oxo 3-(2-trichloro ethoxy) 1-propenyl] cyclopropane carhoxylate. ctp = +42-5° " 2°(c = 0.5% benzene).

Example 32: (S) α-cyano 3~phenoxy benzyl (IR cis) 2,2-dimethyl-3-((Z)-3-oxo 3-(2-chloro ethoxy) 1-propenyl] cyclopropane carhoxylate. α-θ = +39° ~ 4°(c = 0.2% benzene) Example 33·’ (S) α-cyano 3~phenoxy benzyl (IR cis) 2,2-dimethyl-;3-C(Z)-3-oxo 3~(2-methoxy ethoxy) 1-propenyl] cyclopropane carhoxylate. aD = +37.50 ± 2°(c = 1% CHGlj) Example 34: (S) α-cyano 3~pbenoxy benzyl (IR cis) 2,225 -dimethyl-3-[(Z)-3-oxo 3~(BS) 1-cyano ethoxy) 1-propenyl] cyclopropane carhoxylate. aD = +64.5°- 3° (0 = 0.3% CHClj) 514 51 Example 35· (S) α-cyano 3-phenoxy benzyl (15 cis) 2,2-diaethyl-3-C(Z)-3-oxo 3-(2-fluoro ethoxy) 1-propenyl] cyclopropane carboxylate. » +48° (c 0.2% benzene).

Example J6: (S) α-cyano 3-phenoxy benzyl (15 cis) 2,2-dimethyl-3-C(Z)-3-oxo 3~phenethoxy 1-propenylJ cyclopropane carboxylate.

D -+46° 2 2.5° (c - 0.5% benzene).

Example 37: (S) «-cyano 3-phenoxy benzyl (15 cis) 2,210 -dimethyl-3-C(Z)-3-0x0 3(2,2-dimethyl dioxolanyl 4-(BS)-methoxy) 1-propenyl] cyclopropane carboxylate. aD a +46° 2 2°(c a 0.7% benzene). 6) (ES) α-cyano 3-phenoxy benzyl (IE cis) 2,2-dimethyl-3-C(Z)-3-hydroxy 3~oxo 1-propenylJ cyclopropane carboxylate and the corresponding alcohol.

Example 38: (BS) α-cyano 3-phenoxy benzyl (IE cis) 2,2-dimethyl-3-C(Z)-3-0x0 3~(2-dimethyl amino ethoxy) 1-propenyl] cyclopropane carboxylate. aD - +23° 2 5»(c a 0.2% CHClj) The- (ES) α-cyano 3-pbenoxy benzyl (IE cis) 2,2-dimethyl-3-[(Z)-3-hydroxy 3-0x0 1-propenyl] cyclopropane carboxylate, used at the beginning of the previous Example, was prepared in a manner similar to that for the (S) a-cyano 3-phenoxy benzyl ester of Preparations IV and VII. 7) (E) α-methyl 3~phenoxy benzyl (IR cis) 2,2-dimethyl-3-[(Z)-3-hydroxy 3~oxo 1-propenyl] cyclopropane carboxylate (Preparation VIII) and the corresponding alcohol.

Example 39: (5) α-methyl 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-C(Z)-5-oxo 3~(2-methoxy ethoxy) 1-propenyl] cyclopropane carboxylate.

NMR CLClj p.p.m. 1.22 - 1.25 protona of the methyls at 2 of the cyclopropane, 1.4-5 - 1,55 protons of the methyl of the ester at 1 of the cyclopropane, ·? to 6.0 proton of the benzyl, 3.42 protons of the methoxyl, 4.22 to 4.38 protons at 1 of the ester at 3 of the cyclopropane, 3.55 bo 3.72 protons at 2 of the ester at 3 of the cyclopropane, .85 - 6.05 and 6.32 to 6.8 ethylenic protons.

Example 40; (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-i(Z)-3-0x0 3-(l~methoxy 1-trifluoromethyl ethoxy) 1-propenyl] cyclopropane carboxylate.

Under inert atmosphere are agitated 1.02 g of (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3~C(Z)-3-chloro· 3-oxo 1-propenyl) cyclopropane carboxylate and 9 cm^ of methylene chloride. 1.12 g of 1-methyl 1-trifluoromethyl ethanol are added and the agitation is maintained for 48 hours at ambient temperature. The whole is concentrated to dryness under reduced pressure, the residue is chromatographed on silica and eluted with a mixture: hexane / ethyl ether (8:2) and 250 mg of expected product are obtained, M.Pt.~ 59°C. "j = +57° - 2° (c » 0.4% benzene) The (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-((Z)-3-chloro 3-oxo 1-propenyl] cyclopropane carboxylate used at the start of Example 40, was prepared by the action of thionyl chloride on (S) a-cyano 3"phenoxy benzyl (IR cis) 2,2-dimethyl-3-C(Z)-3-hydroxy-3-oxo 1-propenyl] cyclopropane carboxylate, Preparation VII. Example 41: (S) a-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-5-C(Z)-5-oxo 5-(l-trifluoromethyl 1-methyl IQ propyloxy) 1-propenyl] cyclopropane carboxylate. 900 mg of (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3~[(Z)-3-chloro-3roxo 1-propenyl] cyclopropane carboxylate are dissolved in 3 cm^ of methylene chloride, cm-5 of 1-trifluoromethyl 1-methyl propanol is added and the whole is agitated for 16 hours at ambient temperature under inert atmosphere and away from humidity. After 3 days at ambient temperature, the reaction mixture is washed with a saturated aqueous solution of sodium bicarbonate then with water, dried and concentrated to dryness. The residue is chromatographed on silica and eluted with a mixture: hexane / ethyl ether (8:2) and 570 mg of expected product are obtained.

Example 42: (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dlmethyl-3-C(Z)-5-oxo 3-(2,3-dihydroxy propyloxy) 1-propenyl] cyclopropane carboxylate. 4.65 g of (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-(2,2-dimethyl dioxolanyl 4-(H£>)-methoxy) 1-propenyl] cyclopropane carboxylate (Example 37), 1451 cm^ of dioxan, 9 cm^ of water and 0.45 g of paratoluene sulphonic acid are heated to reflux for 45 minutes. The majority of the dioxan is eliminated hy distillation at 40°C under reduced pressure and the residue is taken up with 150 cm^ of methylene chloride and 25 cm^ of water.

This is agitated and decanted and the organic phase is washed with water, dried and concentrated to dryness under reduced pressure. The residue is chromatographed on silica and eluted with a mixture: cyclohexane / ethyl acetate (3:7) and 3·85 g of expected product are obtained. aD a +530 ί 2.5° (0 = 0.5% CHClj).

Example 43.· (RS) α-cyano 3-phenoxy benzyl (15 cis) 2,2-dimethyl-3-[(Z)-3-oxo 3~(2-tetrahydropyranyloxyethoxy) l-propenyl] cyclopropane carboxylate.

Stage A: £RS)_a-c£ano_32Phenoxy_benzyl £lR £is)_2A2-djjqethylZ.52(£z2-^,-£xo_ ^-^_2-t£trahydropyranjlo,xyetho,X2)_l^pr,opynyl]_ cycl£propane_carboxylajte_;_ Work is carried out in a manner similar to that described in Stage A of Example 7: starting with 2.3 g of (RS) α-cyqno 3_pbenoxy benzyl (IR ci's) 2,2-dimethyl-3-C(Z)-3-hydroxy-3~oxo 1-propynyl] cyclopropane carboxylate and 7·5 g of 1-hromo 2-(2-tetrahydropyranyl) oxy ethane. 1.8 g of expected product are obtained after chromatography on silica in the mixture: cyclohexane / ethyl acetate (75:25). Stage. B: £RS)_a£c^ano_33phenoxy_b£nzyl £lR ci£)_2A2-dimeth2l£32.(i.Z2-J.-£X£ ^-^-t^trahydropjranjloxjeihoxj) l-propenyl]_ eyel£p£O£ane_carboxylatei S14S1 Work is carried out in a manner similar to that described in Stage B of Example 7, starting with the product obtained in Stage A above. After purification by chromatography in the mixture: cyclohexane / ethyl acetate (80:20), 1.3 g of expected product are obtained. oD - +33° ί 1° (c . 1% CHClj) The (BS) α-cyano 3-phenoxy benzyl (IB cis) 2,2-dimethyl~3-[(Z)-3-hydroxy 3-oxo 1-propynyl] cyclopropane carhoxylate, used at the beginning of the previous Example, was prepared in a manner similar to that for the (S) a-cyano 3-phenoxy benzyl ester of Preparation IV.

Example 44: (BS) a-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-(2-hydroxy ethoxy) 1-propenyl] cyclopropane carhoxylate. 0.85 6 of product obtained in Example 43, 17 cm^ of ethanol, 5 om^ of dioxan, 1 cm^ of water and 4 cm^ of 2N hydrochloric acid and mixed then agitated at 20°0 for 3 hours. 1 cm'* of triethylamine is then added, the whole is evaporated to dryness, taken up with a water/ice mixture and extracted with methylene chloride, the extract is washed with water and dried and the solvent is evaporated. The residue is chromatographed on silica, eluting with a mixture: cyclohexane / ethyl acetate (65:35) and 0.65 g of expected product is obtained. aD « +42.50 1 2.5° (c - 0.5% CHCl^) The following compounds can also be obtained according to the process of the invention, starting with acids and corresponding alcohols: Si 451 - 3-phenoxy benzyl (IE cis) 2,2-dimethyl-3-C(Z)-3-oxo 3-(1,1,1,3,3,3-hexafluoro propoxy) propenyl] cyclopropane carboxyiate, D = +26.5° i 2-5° (c = 0.% CHClj) - (S) α-cyano 3-phenoxy 4-fluoro benzyl (IE cis) 2,2-dimethyl _3_[(Z)-3-oxo 3-(l,l,l,3,3,?-hexaflutfr0 propoxy) propenylJ cyclopropane carboxyiate, aD = +27° c = 0.8% benzene).

Preparation IV: (S) α-cyano 3-phenoxy benzyl (IR cis) 2,2-dimethyl-3-(3-oxo 3-hydroxy 1-propynyl) cyclopropane carboxyiate.

Stage A: Tert2butyl_(lR_cis)_ 2,£-dimeth2l^£2-carboxy_ £thynyl]_cycloprppane £a£boxylate. g of tert-butyl (IR cis) 2,2-dimethyl 3-(2,2-dibromovinyl) cyclopropane carboxyiate are introduced into 175 .cm^ of anhydrous tetrahydrofuran. 60 cn? of a 20% solution of butyl lithium in cyclohexane are then added at -65°C. The whole is agitated for 1 hour at -60°C then a current ofcartnn dioxide is bubbled in for an hour and a half and the reaction mixture is poured into iced water to which has been added N sodium hydroxide. The whole is washed with ether. The alkaline aqueous phase is acidified to pH 4 and extracted withebher. The organic phases are dried and brought to dryness under reduced pressure. A product is thus obtained which is recrystallised from petroleum ether, (B.Pt. 60-80°C). 8.3 g of the product sought are then obtained, melting at 144°C.

S14BJ NMS CDC1, p.p.m. 1.22 and 1.37 1.78 1.4-7 8.25 protons of the methyls at 2 of the cyclopropane, proton at 1 and 3 of the cyclopropane, protons of the tert-butyl, proton of the group -C-OH 0 Stage B: Te£t-but2l_(lR_cisJ). 2,2-dimeth£l_3x(£,2,2-£ri-_ chloroethoxycarbonyl ethynyl) cyclopro^ane^arboxylatej. 6.2 g of dieyclohexylcarbodiimide are introduced into a solution containing 7-15 E of tert-butyl (IB cis) 2,2-dimethyl 3-(2-earboxyethynyl) cyclopropane carboxylate and 80 mg of dimethylaminopyridine in 35 cm^ of methylene chloride. The reaction mixture is agitated for 10 minutes and 4.5 g of 2,2,2-trichloroethanol are added. The whole is maintained under agitation for 1 hour and the precipitate formed is removed by filtration. The filtrate is washed with N hydrochloric acid, then with water until neutral, it is dried and it is brought to drynesS. 14 g are obtained of an oil- which is chromatographed on silica, eluting with the mixture: benzene / ethyl acetate (97:3)· 9 g of the product sought are thus isolated, melting at 7O-71°C· Stage C: (lR_cisX 2,2-dime£h£l_3z.(2,2,2-trichl£r£ethox2carbonyl ethynyl) cyclopro£ane_carboxylic acidx A mixture containing 11.4 g of the product prepared according to Stage B, 120 cm^ of toluene and 300 mg of paratoluene sulphonic acid is taken to reflux for 1 hour.

It is allowed to return to ambient temperature and the reaction mixture is washed with water, it is dried and it is brought to dryness. 9·5 g are thus obtained of the product sought which is used as it is for the following stage. Stage, D: (S)_a£cy;ano_3£phenoxy_b£nzyl _£lfi £i£)_2j2-dimethyl. J."X.2_L2_L2£ti;i£hloro_e_thox2; ^arb^n^^eth^njl^ cyclnpronane_ 2arb£X£late,. 6.2 g of dicyclohexylcarbodiimide are added to a solution containing 9-5 g of the product prepared in Stage C, 30 cm^ of methylene chloride and 3 cm^ of pyridine. The reaction mixture is agitated for half an hour and 6.8 g of (S) α-cyano 3-phenoxy benzyl alcohol are added. The whole is maintained under agitation for an hour and a half.

The insoluble matter formed is removed by filtration. The filtrate is washed with N hydrochloric acid, then with water until neutral. It is dried, it is filtered and it is brough.t to dryness. 15-3 g are obtained of an oil which is chromatographed on silica, eluting with the mixture: benzene / ethyl acetate (97:3)· 12 g of the product sought are thus isolated) melting at- 101°C.

Stage, E: (S)_a-c£ano_3^phenoxy_benzyl £ΐΉ £is,)_24.2£dim£thyl ^-l3£h2dno2£y_3£Oxo_l^p£O£ynyl)_cyOlp£ropane. carbox2rlate,. .9 g of zinc powder are introduced into a solution containing 6.5 g of the product prepared in Stage D, 23-4 cm^ of acetic acid and 2.6 cm^ ofwater. The mixture is maintained under agitation for 1 hour. It is filtered and the filtrate is decanted. The organic phase is washed with water and the aqueous phase is extracted with methylene chloride. The chloromethylenic solutions are combined, dried, filtered and brought to dryness. 4.7 g are thus 514 51 obtained, of crude product used as it is.

Preparation V: Tert-butyl (IR cis) 2,2-dimethyl 3-((2) (3-hydroxy 3-oxo 1-propenyl] cyclopropane oarboxylate. g of tert-butyl (IR cis) 2,2-dimethyl 3(2-carboxy 5 ethynyl] cyclopropane oarboxylate, prepared in Stage A of Preparation IV, in 40 cm^ of ethyl acetate are hydrogenated inthe presence of 0.38 g of 10% palladium hydroxide on barium sulphate and 0.4 cm^ of quinoline.

The whole is filtered, the filtrate is washed with 0.5 H hydrochloric acid, then with water until neutral, dried and concentrated to dryness under reduced pressure and 2 g of the product sought are obtained, melting at 94°C. Preparation VI; (IR cis) 2,2-dimethyl 3-((Z) 3-oxo 3-(2-(1,1,1,3,5.3 hexafluoro) propoxy) 1-propenyl] cyclopropane carboxylic acid.

Stage A: Tert-but2l_(lR_cis). 2,2-dimethyl_3-(£Z). £-oxo £-12^(1,1,1.,£-hexafluoro__pro£Oxy). i-£ropenyl2 £y£lopro£ane_carboxylatex Work is carried out as in Stage A bx Example 9, using 3.6 g of tert-butyl (IR cis) 2,2-dimethyl 3"((Z) 3-hydroxy 3-oxo 1-propenyl] cyclopropane oarboxylate (Preparation V) and 3 g of hexafluoro isopropanol. After elution with a mixture: benzene / cyclohexane (4:6), 4.9 g of expected product are obtained, M.Pt. - 92°C.

. Stage B: (lR_cis). ,2,.2-dimethyl_3-(£Z). j5~£X£ ^£-2(1,1.,^,^ l,^,^-hexafluor°2 £ropox2)_l2pro£enyl]_ojjcj.0£ropan£ £arbox2lic_a£id. are obtained. ) 35ΟΟ. cm1 ) ( 1755 cm1 shoulder ( -1 ( 1744 cm maxi 1695 cm 1627 cm 1380 cm1 shoulder.

(S) α-cyano 5-Phenoxy benzyl (IB cis) Work is carried, out as in Example 11, Stage B, starting with 4.9 g of the product obtained above and 4.2 g of expected product IB (CHOI,) OH mono acid + dimer C conj. ester II 0 acid C=C conj. gem. dimethyl Preparation VII: 2,2-dimethyl 3C(Z) 5-hydroxy 3~oxo 1-propenyl] cyclopropane carboxylate. 4,7- g of (S) α-cyano 3~phenoxy benzyl (1H cis) 2,2-dimethyl 3-(2-carboxy ethynyl) cyclopropane carboxylate (Preparation IV) in 45 cm^ of ethyl acetate are hydrogenated in the presence of 500 mg of 10% palladium hydroxide on barium sulphate and 6.5 cm^ of quinoline. The whole is filtered and the filtrate is washed with N hydrochloric acid, then with water until neutral, dried and brought to dryness. 5-1 g are obtained of an oil which is chromatographed on silica, eluting with the mixture: hexane / ethyl acetate / acetic acid (70:30:1). 3.8 g of the product sought are thus obtained.

Preparation VIII: (B) α-methyl 3-phenoxy benzyl (IB cis) 2,2-dimethyl 5~[(Z) 5-hydroxy 5-oxo 1-propenyl] cyclopropanecarboxylate.

S+age A: (K)_a-m£thyl _}-£henoxy b.e£zZl«_(iH_ci32 2,2-dimeth2l ,£-l5-oxo_3-(2,2,2-£richlor£ ethoxy}. £roj>2PXli £ycl£pro£ane_ £arboxxlate,.

Work is carried out as in Stage D of Preparation IV, using 6 g of (IR cis) 2,2-dimethyl 3-C3~oxo 3-(2,2,2-trichloroethoxy) propynyl] cyclopropane carboxylic acid and 4.1 g of 1-(R)(-3-phenoxy phenyl) ethanol. After chromatography in a mixture: cyclohexane / ethyl acetate (8:2), 4.38 g of expected product are obtained.

Stage B: £R}_ a-metb2l_3^phehoxy_b£n£7l £1R £i£)_2_J2-dim ethyl ^"i3z°x°.J5-hydro^j?ro£y^jJ_c2cj££ropane £arbos2lat£.

To 4.16 g of product obtained above, dissolved in 4 cm^ of methylene chloride, are added 45 cm^ of acetic acid containing 10% of water and 0.53 S °f zinc powder and the whole is agitated for 30 minutes at ambient temperature, then Ο.53 g of zinc powder are added again until the reaction has finished (4 times). After 3 hours' contact, the whole is filtered and extracted with methylene chloride. The organic phase is washed with water, dried and concentrated to drynes's by azeotropic distillation with toluene and 3.05 g of expected product are obtained.

Stage C: a-me£hyl_3^phenoxy_b£nzyl £1R £is)_2χ2χάΰπβthyl. li.iZ)_3£h2dro2gy_3-oxo_l2j)ro£enyl]_c£cj.o£r£P£ne £arboxyl£te.

Work is carried out as in Stage B of Example 7, starting with the product obtained in Stage B above, and 2.9 g of crude expected product are obtained, used as it is.

Examples of Compositions Example A; Preparation of a soluble concentrate.

A homogeneous mixture is made up, consisting of: Product of Example 1....................... 0.25 g Piperonyl butoxide ......................... 1 g Tween 80 ................................... 0.25 S Topanol A..................................0.1 g Water......................................98.4 g Example B: Preparation of an emulsifiable concentrate.

Intimately mixed are: Product of Example Ϊ...................... 0.015 S Piperonyl butoxide ........................ 0.5 g Topanol A................................. 0.1 g Tween 80 .................................. 3· 5 B Xylene .................................... 95-885 g Example C: Preparation of an emulsifiable concentrate.

A homogenous mixture is made up, consisting of: Product of Example 1 ..................... 1.5 g Tween 80 ................................. 20 g Topanol A................................. 0.1 g Xylene .................................-- 78.4 g Example D: Preparation of a smoke-producing composition Homogenously mixed are: Product of Example 1 ..................... 0.25 g Tabu powder .............................. 25 g Cedar-needle powder ...................... 40 g Pine-wood powder..... ....................... 33*75 g Brilliant green .......................... 0.5 g p-nitrophenol ............................ 0.5 g Study of the activity of the compounds according to the invention on parasites. 1): Study of_the_l£thal e£t_on houseflies The test insects are female houseflies, 4/5 days old. 5 Work is carried out by topical application of 1 μΐ of acetonic solution of the product to the dorsal thorax of the insectsby means of the Arnold microymanipulator. 50 individuals per dose and per treatment are used. The mortality check is carried out twenty-four hours after treatment.

The result ob'qained, expressed in ID 50 or dose (in nanograms) necessary to kill 50% of the insects, is as follows: Product of example LD 50 (ng per individual 1 1.115 23 0.962 29 0.825 Conclusion: in the test used the products of Examples 1, 23 and 29 show remarkable activity. 2) Study of_the_effect £n_larvae of_Spodo£te.ra .littoraliSj. The tests are carried out by topical application of an acetonic solution of the product to be tested by means • of the Arnold micro-manipulator to the dorsal thorax of the larvae. 15 larvae per dose of product to be tested are used. The larvae used are larvae of the fourth larval stage 514 51 that is to say about 10 days old when they are raised at 24°C and 6% relative humidity. After treatment the individuals are placed on an artificial nutrient medium (Poitout medium).

The mortality check is carried out 48 hours after treatment.

The experimental result obtained is as follows: Compound of LD 50 example (ng per individual) 1 4.699 55 Ο.544 Conclusion: in the test used, the products of Examples 1 and 35 show good activity. 3): Study of_the_Jmo£kydown actiyity_pn the hous£fly.j.

The test insects are female houseflies, 4/5 days old.

Work is carried out by direct spraying in a Kearns and March chamber, using as solvent a mixture in equal volumes of acetone and isopar L (amount of solution used 2 x 0.2 cm^) About 50 individuals per dose of treatment are used. Checks are carried out every minute up to 10 minutes, then at 15 minutes and the KT 5θ is determined by the usual methods.

The results obtained are as follows: Product of example KT 50 in minutes Concentration g/1 1 5-554 1 2 3.608 0.25 26 1-550 0.25 50 3.498 1 55 2.894 1 Conclusion; in the test used, the products of Examples 1, 3, 26, 30 and 35 show good activity. 4) : Studj of_the_ac,tivit2 by_tarsal contact £n_the_Germani£ £ockroach £c£m£ound £f_3xainple_l}..

The test insects are male Germanic cockroaches (Blatella germanica). Work is carried out by depositing an acetonic solution of fixed concentration on to the bottom of a Petri dish, 20 cm in diameter. After drying, male cockroaches per concentration are allowed to stay for 1 hour then the insects are transferred to a healthy medium and their mortality is checked at 24 hours, 48 hours and 3 and 5 days.

The result, expressed in lethal concentration 5θ p (LC 50) gives, for the product considered, 0.216 mg/m . Conclusion: according to the. test used the product shows very good’ activity.

) : Ac£ivity_on Tetranjchus, urtica£. (compound of Example 1) Adulti£idal test^ Bean plants comprising two cotyledonous leaves are used. These plants are treated with a Pisher pistol with an acetonxc solution of the product. After drying, 25 females of the acaridan Tetranyohus urticae are deposited per leaf, that is $0 individuals per dose tested per plant. Efficiency checks are carried out after 1, 24, 48 and 72 hours' contact.

At the dose of 2.8 mg/1 the product shows very good activity.

Claims

CLAIMS 1. To 8 carbon atoms, to the action of 2,2,2-trichloroethanol to obtain the compound of formula (XII): (XII) in which the cyclopropane moiety is of IR cis structure, 15 whicn is subjected to the action of an acid hydrolysis agent to obtain the compound of formula (XIII): (XIII) in which the cyclopropane moiety is of 1R cis structure which is subjected, to the action of an alcohol of formula (III): A'-OH (III) in which A' keeps the same meaning as in Claim 1, to obtain the compound of formula (XIV): in which the cyclopropane moiety is of 1R cis structure, which is subjected to the action of an agent for cleaving the ester function borne by the acetylenic carbon to obtain the compound of formula (XV): COgH in which the cyclopropane moiety is of 1R cis structure which is subjected to the action of a mild hydrogenation agent to obtain the compound of formula (XI). 17. Process according to Claim 15 or 16, characterised 15 in that a compound of formula (XV): COjA' (XV) in which the cyclopropane moiety is of 1R cis structure and in which A' is defined as in Claim 1, is subjected to the action of an esterification agent, to obtain the compound of formula (X): in which the cyclopropane moiety is of 1R cis structure and in which R and A' are defined as in Claim 1, which is subjected to the action of a mild hydrogenation agent, to obtain the compound of formula (I*). 13. Process for preparing the compounds of formula (I'), 10 in which S represents an alkyl radical substituted by one or more hydroxy radicals, according to which there are prepared firstly by a process according to any one of Claims 10 to 17, compounds of formula (I'), in which R represents an alkyl radical substituted by one or more 15 protected hydroxy radicals, and characterised in_that these compounds are subjected to the action of an acid hydrolysis agent. 19. Use of the compounds of formula (I'), as defined in any one of Claims 1 to 12, in the control of parasites of 20 plants, parasites of premises and parasites of warmblooded animals. 23. Compositions intended for the control of parasites of plants, parasites of premises and parasites of warm-blooded animals, characterised in that they contain as 25 active principle at least one of the products defined in 98 51-45,1 any one of Claims 1 to 9. 21. Insecticidal compositions containing as active principle at least one of the products defined in any one of Claims 1 to 8. 22. Insecticidal compositions containing as active principle at least one of the products defined in Claim 9. 23. Compositions intended for animal feeding containing as active principle at least one of the products defined in any one of Claims 1 to 9 . 24. Associations endowed with insecticidal, acaricidal or nematocidal activity, characterised in that they contain as active substance on the one hand one at least of the cottpounds of general formula (I‘) as defined in claim 1 and on the other hand one at least of the pyrethrinoid esters selected from the group constituted by the esters of allethrolone, of

1. In all the possible isomeric forms or in the form of mixtures, the compounds of formula (I'): EOgC—CH =* in which the cyclopropane moiety is of IR cis structure 5 and the double bond is of Z geometry and in which A' represents: - either an alkyl radical containing from 1 to 18 carbon atoms, - or a benzyl radical possibly substituted by one or more 10 radicals selected from the group constituted by the alkyl radicals containing from 1 to 4 carbon atoms, the alkenyl radicals containing from 2 to 6 carbon atoms, the alkenyloxy radicals containing from 2 to 6 carbon atoms, the alkadienyl radicals containing from 4 to 8 carbon atoms, 15 the methylene dioxy radical and the halogen atoms, - or a group: in which the substituent represents a hydrogen atom or a methyl radical and the substituent Eg represents a In which, a represents a hydrogen atom or a methyl radical and Ej represents the radical -CH 2 -CH=CH 2 , in which a represents a hydrogen atom or a methyl radical, 10 Rj keeps the same meaning as before and R'and R'g, being the same 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, an alkyloxycarbonyl group containing from 2 15 to 5 carbon atoms or a cyano group, - or a group: Η in which B represents an oxygen or sulphur atom or a group il -C - or -CHg- and E^ represents a hydrogen atom, a radical -C s N, a methyl radical, a radical -CONHg, a radical -CSNHg or a radical -0 = CH, E^ represents a halogen atom 2. ,2-dimethyl 3-(2,2-dichlorovinyl)-cyclopropane-1— -carboxylic acid; by the esters of a-cyano-3-phenoxyhenzyl alcohol with 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropane-l-carboxylic acid; by the esters of' 3-phenoxybenzyl alcohol with 2-parachlorophenyl-2-isopropyl-acetic acid; and by the esters of allethrolone, of 3,4,5,6-tetra99 hydrophthalimidomethyl alcohol, of 5-benzyl-3-furylmethyl alcohol, of 3-phenoxybenzyl alcohol and of a-cyano3-phenoxy benzyl alcohol with 2,2-dimethyl 3-(1,2,2,2tetrahaloethyl) cyclopropane-l-carboxylic acids, in 2,2-dimethyl-3C(Z) 3-oxo-3“(2,2,2-trifluoroethoxy)-1-propenyl]20 cyclopropane-carboxylate, and - (IS) 2-methyl-4-oxo-3 _ (2-propenyl)-2-cyclopenten-l-yl (IR cis) 2,2-dimethyl-3C(Z)-3-0x0-3~(2,2,2-trifluoroethoxy)l-propenyl]-cyclopropane-carboxylate. 10. Process for preparing the compounds of formula (I*), 25 as defined in any one of Claims 1 to 9, characterised in that an acid of formula (II): 514 51 EO 2 C — ON (II) in which the cyclopropane moiety is of 1R cis structure and the double bond of Z geometry and in which R keeps the same meaning as in claim 1, or a functional derivative of this acid is reacted with an

2. In all the possible isomeric forms or in the form of mixtures, the compounds of formula (I*) as defined in Claim 1, corresponding to the formula (I): (I) in which the structure of the cyclopropane moiety is 1R cis and the geometry of the double bond is Z and in which A represents: - either an alkyl radical containing from 1 to 18 carbon 15 atoms, - or a benzyl radical possibly substituted as defined in Claim 1, in which the substituents Εχ and Eg are as defined in Claim 1, - or a group: S'. in which a, B'p E' 2 - or a group: and. Β^ are as defined in Claim 1, < R 5 5 n II 3. ,4,5,6-tetrahydrophthalimidomethyl alcohol, of 5-benzyl 3-furylroethyl alcohol, of 3-phenoxybenzyl alcohol and of α-cyano 3-phenoxybenzyl alcohol with chrysanthemic acid; by the esters of 5 - benzyl-3 - furyImethyl alcohol with 2,2-dimethyl - 5-(2-oxo _ 3-tetrahydrothiophenylidene methyl) cyclopropane-1-carhoxylic acids·, by the esters of 3-phenoxy benzyl alcohol and of α-cyano - 3-phenoxybenzyl alcohol with - (3-propargyl-2,5-dioxoimidazolidinyl)-methyl (IR cis) 3-oxo-3“(2-fluoro ethoxy)-l-propenyl]-cyclopropane carboxylate,

3. The compounds of formula (I*), as defined in claim 1 or claim 2 in which A. represents an α-cyano -J -phenexy benzyl group, in S, E or ES form.

4. The compounds of formula (I 1 ), as defined in 5. Claims 10 to 18 and 30, 32. A process for the preparation of a compound of formula (II) , (VI) , (IX) or (X) (as defined in claims 10, 12 and 14) substantially as herein described. 33. Compounds of formulae (II), (VI), (IX) and 5 which halo represents a fluorine, chlorine or bromine atom, it being understood that the compounds (I') can exist in all their possible steroisomeric forms, the same as the acid and alcohol moieties of the pyrethrinoid esters above. 10 25, As medicaments, the compounds defined in any one of Claims 1 to 9. 26. Pharmaceutical compositions containing, as active principle, one at least of the medicaments defined in Claim 25 . 15 27 . As intermediate products necessary for the preparation of the compounds of formula (I 1 ), as defined in Claim 1, the compounds of formulae (II) and (VI) defined in Claim 10 and in Claim 12. 28, As intermediate products necessary for the 20 preparation of the compounds of formula (1 1 ) , as defined in Claim 1, the compounds of formulae (IX) and (X), defined in Claim 14. 29. A compound of· formula (1 1 ) as claimed in claim 1 as herein specifically disclosed in any of the Examples. 25 30. A process for the preparation of a compound as 100 claimed in claim 1 substantially as herein described in any one of the Examples. 31. Compounds of formula (I') as claimed in claim 1 whenever prepared hy a process as claimed in any one of 5 to obtain the compound of formula (I*), - or is subjected firstly to the action of a mild in which B is defined as before, in tfiich the cyclopropane 10 moiety is of 1R cis structure and the double bond has the geometry Z, then, if appropriate, in the form of a functional derivative, to the action of an alcohol (III), to obtain the compound of formula (I 1 ). 15.. Process for preparing the compounds of formula (I 1 ), 15 as defined in Claim 1, characterised in that a compound in which the cyclopropane moiety is of 1R cis structure and in which the double bond has the geometry Z, is subjected to the action of an esterification agent, to obtain the corresponding compound of formula (I*)· 5 16. Process according to Claim 15, characterised in that the compound of formula (XI) is prepared by subjecting an acid of formula (V): in which the cyclopropane moiety is of 1R cis structure and 10 in which alk represents an alkyl radical containing from 5 in which Hal represents a halogen atom and R keeps its previous meaning, to obtain directly the compound of formula (VI): in which the cyclopropane moiety is of IR cis structure, then the compound of formula (VI) is subjected to the action of a mild hydrogenation agent, to obtain the compound of formula (VII): (νπ) 514 51 in which the cyclopropane moiety is of 1R cis structure and in which the double bond has the geometry Z, which is subjected to the action of an acid hydrolysis agent capable of cleaving selectively the ester function on the carbon at position 1 of the cyclopropane, to obtain the corresponding compound of formula (II). 13. Process according to Claim 12, characterised in that firstly the compound of formula (V) is subjected to the action of a mild hydrogenation agent to obtain the compound of formula (VIII): (VIII) in which the cyclopropane moiety is of 1R cis structure and in which the double bond has the geometry Z, which is subjected to the action of an esterification agent, to obtain the corresponding compound of formula (VII): R0 2 C - CH* Ci C0 2 alk (m) in which the cyclopropane moiety is of 1R cis structure and in which E keeps its previous meaning, then the synthesis is carried out as described in Claim 12. 14. Process according to Claims 10 and 12, characterised 5 in that a compound of formula (VI): in which the cyclopropane moiety is of 1R cis structure and in which E and aTk are defined as in Claims 10 and 12 , is subjected to the action of an acid hydrolysis agent 10 capable of cleaving selectively the ester function at position 1 of the cyclopropane, to obtain the compound of formula (IX) in which the cyclopropane moiety is of 1R cis structure and in which E is defined as before, which 15 - either is subjected, if it is in..the .form- of a functional derivative, to the action of an alcohol of formula (III): A'-OH (III) in which A' keeps the same mean:ng as in Claim 1, to obtain 20 the compound of formula (X): in which the cyclopropane moiety is of 1R cis structure and In which E and A* keep the same meaning as before, which is subjected to the action of a mild hydrogenation agent, 5 alcohol of formula (III) A’-OH (III) in which. A* keeps the same meaning as in Claim 1, to obtain the corresponding compound of formula (I 1 ). 11. Process according to Claim 10, characterised in that 10 the compounds of formula (II) are prepared by subjecting, in an organic solvent, a compound of formula (B^): (Β χ ) in the form of a cis lactone, to the action of a compound, of formula (B 2 )i CH - C OE (b 2 ) in which 5 keeps its previous meaning, to obtain the corresponding compound of formula (II): BOgC CH (II) in which the cyclopropane moiety is of 1R cis structure, 5 in the form of a mixture of isomers E and Z, which is separated, into each of the isomers. 12. Process according to Claim 11, characterised in that the compounds of formula (II) are prepared by reacting a compound of formula (IV): in which the cyclopropane moiety is of 1R cis structure and in which Hal represents a halogen atom and alk represents an alkyl radical containing from 1 to 20 carbon atoms, firstly with an alkaline agent capable of removing the 15 halogen atoms, then secondly - either with an agent capable of introducing the carboxylic group to obtain the compound of formula (V): HOgC — C 3 (V) C0 2 alk in which the cyclopropane moiety is of 1R cis structure, which is subjected to the action of an esterification agent to obtain the compound of formula (VI): eo 2 c - C = C in which the cyclopropane moiety is of 1R cis structure and in which R keeps the same meaning as before, - or with a derivative of formula: Hal - C0 2 R

5. The compounds of formula (I'), as defined in any one of Clains 1 to 4, in which E represents an alkyl 10 radical containing from 1 to 18 carbon atoms substituted by one or more functional groups mentioned in claim 1 · 5 claim 1 or claim 2 in which A represents a 2-methyl-4-oxo-3-(2-propenyl) 2-cyclopenten-l-yl group, in S, E or ES form. 5 - or a group: and R is as defined in Claim 1. 514 31 5 in which B represents an oxygen atom or a group -C or -CH 2 -, is as defined in Claim 1, B^ represents a chlorine atom or a methyl radical and n represents a number 0, 1 or 2, - or a group: z\ XX χχ - or a group: in which the substituents Βθ, 5?, Rg, Rg and S/I are as defined in Claim 1, 5 or R represents a pyridinyl, furanyl, thiophenyl, oxazolyl or thiazolyl radical. 5 in which R-^ is defined as above, each of the R^'s represents independently an alkyl group containing from 1 to 4 carbon atoms, an alkoxy group containing from 1 to 4 carbon atoms, an alkylthio group containing from 1 to 4 carbon atoms, an alkyl sulphonyl group containing from 1 to 4 carbon atoms, 10 a trifluoroaethyl, 3,4-methylene dioxy, chloro, fluoro or bromo group, p represents a number 0, 1 or 2 and B' represents an oxygen atom or a sulphur atom and R represents an alkyl radical containing from 1 to 18 carbon atoms substituted by one or more identical or different groups chosen from halogen atoms, the OH and SH groups, the OR' and SR' groups in which R' represents an alkyl radical containing from 1 to 8 carbon atoms, the groups .R NO, or -N in which R and R', being identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 8 carbon atoms, the groups CTN, SO-gH and PO^ and the 9 rou P s COalkg, SC^alky^ and S0 3 ~ alk 3 in which alkg, alk 2 and alk 3 represent alkyl radicals containing from 1 to 18 carbon atoms, or R represents an alkyl radical containing from 1 to 18 carbon atoms substituted by an aryl radical, itself possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 8 carbon atoms, by one or more CF 3 , OCF 3 or SCF 3 groups, or by a group (G): (G) or R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted on two adjacent carbons by a group (Gg) / c \ «9 — Ο H 20 or substituted by a group 084 or R represents an aryl group containing from 6 to 14 carbon atoms, possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 8 carbon atoms or by a CFj, OCF 3 or SCFj group, 5 - or a group: - or a group: in which represents a hydrogen atom or a radical CN, R 12 represents a radical -CHg- or an oxygen atom and R^ represents a thiazolyl Or thiadiazolyl radical of which 10 the bond with -CH- can be at any one of the available positions, R 12 bonded, to included between the sulphur atom - or a group: ®11 t5le 0 8x15011 atom and a nitrogen atom, a hydrogen atom or a radical OT, in which represents - or a group: in which ls defined as above and the benzoyl radical is at position 3 or 4, - or a group: ®16 in which R^ represents a hydrogen atom or a methyl, ethynyl or cyano radical and R^ and R^g, being different, represent a hydrogen, fluorine or bromine atom, - or a group: 5 or a methyl radical and n represents a number 0, 1 or 2 - or a group: -A N Jn - or a group: hydrogen atom, a chlorine atom or a methyl radical and in which S/I symbolises an aromatic ring or an analogous dihydro or tetrahydro ring,

6. The compounds of formula (I'), as defined in Claim 5 characterised in that E represents an alkyl radical substituted by one or more halogen atoms. 15

7. The compounds of formula (I'), as defined in Claim 6 , characterised in that E is substituted by one or more fluorine atoms.

8. The compounds of formula (I 1 ), as defined in Claim 7, in which E represents a group CHgCE^.

9. Any one of the compounds of formula (I') of which the names are as follows: - (S) α-cyano-3-phenoxy-benzyl (IR ois) 2,2-dimethyl-3C(Z)3-(2,2,2-trifluoroethoxy)-5-oxo Ί-propenyl]-cyclopropane 5 carboxylate, - (S) a-cyano-5-phenoxy-benzyl (IR cis) 2,2-dimethyl-3C(Z)~ 3-oxo-3-(2-(1,1,1,3,3,3-hexafluoro)-propoxy)-1-propenyl]cyclopropane-carboxylate, - (R) α-ethynyl-5-phenoxy-benzyl (IR cis) 2,2-dimethyl 10 3[(Z)-3“OXo _ 3-(2,2,2-trifluoroethoxy)-1-propenyl]cyclopropane-carboxylate, - (RS) cyano-6-phenoxy-2-pyridyl methyl (IR cis) 2,2-dimethyl-3t(Z)-3-oxo-3-(2,2,2-trifluoroethoxy)-1-propenyl]cyclopropane-carboxylate, 15 - (S) α-cyano-3-phenoxy benzyl (IR cis) 2,2-dimethyl-3((Z) _

10. (X) whenever prepared by a process as claimed in claim 32.