NZ197175A

NZ197175A - Cyclopropane carboxylic acid derivatives and pesticidal compositions:intermediates

Info

Publication number: NZ197175A
Application number: NZ197175A
Authority: NZ
Inventors: J Martel; J Tessier; A Teche
Original assignee: Roussel Uclaf
Priority date: 1980-05-23
Filing date: 1981-05-22
Publication date: 1984-08-24
Also published as: IE52150B1; FI78902B; JPH05306248A; DD206731A5; DK163918B; DK163918C; JPH0699354B2; GR81534B; IE811151L; EP0041021B1; ES8300080A1; IL62914A0; DD159068A5; FI78902C; FI811566L; CA1242647A; JPS60214761A; PT73078B; JPS6248660B2; ES8304914A1

Abstract

1. Claims (for the contracting States : BE, CH, DE, FR, GB, IT, LI, LU, NL, SE) In all the possible isomer forms, the compounds with the formula (I') : see diagramm : EP0041021,P51,F1 in which the double bond has Z geometry, the cyclopropane copula is of 1R cis structure and A' represents : either an alkyl radical containing 1-18 carbon atoms, or a benzyl radical possibly substituted by one or more radicals chosen from the group constituted by alkyl radicals containing 1-4 carbon atoms, alkenyl radicals containing 2-6 carbon atoms, alkenyloxy radicals containing 2-6 carbon atoms, alkadienyl radicals containing 4-8 carbon atoms, the methylenedioxy residue, and the halogen atoms, or a see diagramm : EP0041021,P51,F2 group, in which the substituent R1 represents a hydrogen atom or a methyl radical and the substituent R2 represents a monocyclic aryl or a -CH2 -C -= CH group and notably a 5-benzyl-3-furylmethyl group, or a see diagramm : EP0041021,P51,F3 group in which R3 represents an aliphatic organic radical containing 2-6 carbon atoms and one or more carbon-carbon unsaturations and notably the radicals -CH2 -CH=CH2 , -CH2 -CH=CH-CH3 , -CH2 -CH=CH-C2 H5 , -CH2 -CH=CH-CH=CH2 , or a see diagramm : EP0041021,P51,F4 group, in which R3 retains the same significance as previously, each of R'1 and R'2 , identical or different, represents a hydrogen atom, a halogen atom, an alkyl radical containing 1-6 carbon atoms, an aryl radical containing 6-10 carbon atoms, an alkyloxycarbonyl group containing 2-5 carbon atoms, or a cyano group, or a see diagramm : EP0041021,P51,F5 group, in which B represents a CH2 group, or a C=O group, or a hetero element chosen from oxygen and sulphur, R4 represents a hydrogen atom, 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, and notably the 3-phenoxybenzyl, alpha-ethynyl-3-phenoxybenzyl, 3-benzoylbenzyl, 1-(3-phenoxyphenyl) ethyl or alpha-thioamido-3-phenoxybenzyl groups, or a see diagramm : EP0041021,P52,F1 group, or a see diagramm : EP0041021,P52,F2 group, in which each of the substituents R6 , R7 , R8 , R9 represents a hydrogen atom, a chlorine atom, or a methyl radical and in which S/I signifies an aromatic ring or a similar dihydro or tetrahydro ring, or a see diagramm : EP0041021,P52,F3 group, or a see diagramm : EP0041021,P52,F4 group, 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 thiadiazolyl radical of which the bond with see diagramm : EP0041021,P52,F5 may be found at any one of the available positions, R12 being linked to R11 by the carbon atom situated between the sulphur atom and a nitrogen atom, or a see diagramm : EP0041021,P52,F6 group, or a see diagramm : EP0041021,P53,F1 group in which R13 represents a hydrogen atom or a CN radical, or a see diagramm : EP0041021,P53,F2 group, in which R13 is defined as above and the benzoyl radical is in position 3 or 4, or a see diagramm : EP0041021,P53,F3 group, in which R14 represents a hydrogen atom, a methyl, ethynyl or cyano radical and R15 and R16 , which are different from one another, represents a hydrogen, fluorine or bromine atom, or a see diagramm : EP0041021,P53,F4 group in which R14 is defined as above, each of the R17 's represents, independently, an alkyl group containing 1-4 carbon atoms, an alkoxy group containing 1-4 carbon atoms, an alkylthio group containing 1-4 carbon atoms, an alkylsulphonyl group containing 1-4 carbon atoms, or 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, linear, branched or cyclic, saturated or unsaturated, containing 1-18 carbon atoms, as well as the mixtures of these isomers. 1. Claims (for the contracting State AT) Preparation process for all the possible isomer forms, of compounds with the formula (I') : see diagramm : EP0041021,P57,F2 in which the double bond has Z geometry, A' represents : either an alkyl radical containing 1-18 carbon atoms, or a benzyl radical possibly substituted by one or more radicals chosen from the group constituted by the alkyl radicals containing 1-4 carbon atoms, the alkenyl radicals containing 2-6 carbon atoms, the alkenyloxy radicals containing 2-6 carbon atoms, the alkadienyl radicals containing 4-8 carbon atoms, the methylene dioxy residue, and the halogen atoms, or a see diagramm : EP0041021,P58,F1 group, in which the substituent R1 represents a hydrogen atom or a methyl radical and the substituent R2 represents a monocyclic aryl or a -CH2 -C -= CH group and notably a 5-benzyl-3-furylmethyl group, or a see diagramm : EP0041021,P58,F2 group, in which R3 represents an aliphatic organic radical containing 2-6 carbon atoms and or more carbon-carbon unsaturations and notably the -CH2 -CH=CH2 , -CH2 CH=CH-CH3 , -CH2 CH=CH-C2 H5 , -CH2 -CH=CH-CH=CH2 radicals, or a see diagramm : EP0041021,P58,F3 group, in which R3 retains the same significance as previously, R'1 and R'2 identical or different, each represent a hydrogen atom, a halogen atom, an alkyl radical containing 1-6 carbons atoms, an aryl radical containing 6-10 carbon atoms, an alkyloxycarbonyl group containing 2-5 carbon atoms, or a cyano group, or a see diagramm : EP0041021,P58,F4 group, in which B represents a CH2 or C=O group, or a hetero element chosen from oxygen and sulphur, R4 represents a hydrogen atom, 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 numerical 0, 1 or 2, and notably the 3-phenoxybenzyl, alpha-ethynyl-3-phenoxybenzyl, 3-benzoylbenzyl, 1-(3-phenoxyphenyl)ethyl or alpha-thiomado-3-phenoxybenzyl group, or a see diagramm : EP0041021,P58,F5 group or a see diagramm : EP0041021,P59,F1 group, in which each of the substituents R6 , R7 , R8 , R9 , represents a hydrogen atom, a chlorine atom or a methyl radical and in which S/I signifies an aromatic ring or a similar dihydro or tetrahydro ring, or a see diagramm : EP0041021,P59,F2 group, or a see diagramm : EP0041021,P59,F3 group 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 thiadiazolyl radical of which the bond with see diagramm : EP0041021,P59,F4 may be found in any of the available positions, R12 being linked to R11 by the carbon atom situated between the sulphur atom and a nitrogen atom, or a see diagramm : EP0041021,P59,F5 group, or a see diagramm : EP0041021,P59,F6 group, in which R13 represents a hydrogen atom or a CN radical, or a see diagramm : EP0041021,P60,F1 group, in which R13 is defined as above and the benzoyl radical is in position 3 or 4, or a see diagramm : EP0041021,P60,F2 group, in which R14 represents a hydrogen atom, a methyl, ethynyl or cyano radical, and each of R15 and R16 , which are different, represents a hydrogen, fluorine or bromine atom, or a see diagramm : EP0041021,P60,F3 group, in which R14 is defined as above, each of the R17 's represents, independently, an alkyl group containing 1-4 carbon atoms, an alkoxy group containing 1-4 carbon atoms, an alkylthio group containing 1-4 carbon atoms, an alkylsulphonyl group containing 1-4 carbon atoms, or 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, linear branched or cyclic, saturated or unsaturated, containing 1-18 carbon atoms, as well as the mixtures of these isomers, characterized in that an acid with the formula (II) : see diagramm : EP0041021,P60,F4 in which the double bond has Z geometry, R being defined as previously, or a functional derivative of this acid, is submitted to the action of an alcohol with the formula (III) : A'OH in which A' retains the same significance as previously, and in this way the corresponding compound with the formula (I') is obtained.

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number 1 97175 '/ * Priority Date{s): .V**:*?. Complete Specification Filed: ££.*]?.*% £o-r£.£t ; ao^S%[oo ) !ias,s: V*1'" '2'4 'AQG'fS84 i^uohcatsen Date: - P.O. Journal, No: .}?k', mil <CaWfj,JX^-Cs^rrs: Patents Form No. 2 ^/j r v " ^ li Sfii t *' NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION "CHEMICAL COMPOUNDS" -f/WE ROUSSEL—UCLAF a French Body Corporate of 35 Boulevard des Invalides, 75007 Paris, France, hereby declare the invention, for which -i/we pray that a patent may Ipe granted to me/us, and the method by which it is to be performed, to be particularly described in and by the following statement:— - 1 - ffeffowarf by paI( | a > - lar The present invention relates to new derivatives of cyclopropane carboxylic acid, their preparation, their use in the control of ftaracita^, febe/ compositions containing them and the new intermediates obtained. The subject of the invention 'is derivatives of cyclopropane carboxylic acid, bearing at position 3 an unsaturated side chain of geometry Z and of structure Derivatives of cyclopropane carboxylic acid bearing at position 3 a chain of structure H H H 1 ICI1 ntr - 2 - but of which the geometry was essentially E, were certainly known. Let us mention, for example, New Zealand Patent 170797 as well as J.Chem.Soc. Perkin I, page 2470, 1974 and Pest. Sci 1_, page 499, 1976. However the side chain geometry of these compounds was predominantly E. In fact, the synthesis processes used to prepare these derivatives lead almost exclusively only to geometry E (see Agr. Biol. Chem 34, page 1119 1970). For these compounds, of which the geometry of the side chain was E, it has not been possible to make evident any remarkable property. It has just been discovered that certain products, of which the side chain of structure Z and of which the cyclopropane moiety is of IR, cis structure, display exceptional insecticidal properties. The subject of the invention is the compounds of formula (I1): H ro2c h (I') in which the double bond has the geometry Z, the cyclopropane moiety is of IR, cis structure, A' represents: either an alkyl radical containing from 1 to 18 carbon atoms, or a benzyl radical^optionally substituted by one or more radicals selected from alkyl radicals containing from 1 to 4 carbon atoms, alkenyl radicals containing from 2 to 6 carbon atoms, alkenyloxy I97i^ - 3 - radicals containing from 2 to 6 carbon atoms, Itrirg alkadienyl radicals containing from 4 to 8 carbon atoms, the methylene dioxy residue, and halogen atoms), or a group: -CHgBg (in which the substituent R^ represents a hydrogen atom or a methyl radical and the substitutent R~ represents a monocyclic aryl^or a group -CH^-CSCH/and especially a 5-benzyl 3~fury line thy 1 group, or a group: 10 (in which R^ represents an aliphatic organic radical containing from 2 to 6 carbon atoms and one or more carbon-carbon unsaturatiora and especially the radicals -ch2-ch=ch2, -ch2-ch=ch-ch5, -ch2-ch=ch-c2h5, -ch2-ch=ch-ch=ch2\ 15 or a group: 1 10*?! 75 ( _ 4 - aiJcvP in which. R-, keeps the foamc/ meaning ae bo-fo-ge and R'-, and cac>> rzprzsenb R*2» being the same or different,/r-^pgesgiit a hydrogen atom, a halogen atom, an alkyl radical containing from 1 to 6 carbon atoms, an aryl radical containing from 6 to oJko ( 10 carbon atoms, an fclkyloxycarbonyl group containing from 2 to 5 carbon atoms or a cyano group), or a group: (in which B represents a group CHp or C=0, or /a hefrcro clemeirg an oC ajj£<rr\ fr»lac-tod grrrih oxygen -aed sulphu^/, R^ represents a hydrogen 10 atom, a methyl radical, a radical -CON^, a radical -CSNH2 or a radical -C=CH and R^ represents a halogen atom IS or a methyl radical and n /ceprpsprits—a number oqual -t^ 0, 1 or ^), and especially the 3-phenoxy-benzyl, a-ethynyl 3-phenoxy-benzyl, 3-benzoyl-benzyl, l-(3-phenoxyphenyl) - j 15 ethyl or a-thiamido-3-phenoxy-benzyl group, or a group: 197175 - 5 - or a group -CH„- , &tcM (in which the substituents Rg, R-,, Rg and R^ tepreserrtt 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 rin^), or a group: 0 -CH2 n-ch2-csch "T i A ra <pn.i or a group: r. 10 -ch-r11 - r12 (in which R1q represents a hydrogen atom or a radical CN, R^2 represents a radical -CH2 or an oxygen atom and R^ represents a thiazolyl or thiadiazolyl radical of which the bond with R-^q can be found at any one of the available -ill- # - 6 - 197175 positions, R-^ "being "bonded to E-^via the carbon atom between the sulphur atom and a nitrogen atom in R^) » or a group: or a group: 5 (in which represents a hydrogen atom or a radical CN^ or a group: / ^ 0 II c 3 2 r\ in which -R^ is defined as above^ or a group: 1 •at- $ tr it 4 <£jt 7 (in which R^ represents a hydrogen atom or a methyl, ethynyl or cyano radical and R^ and being different, each represents a hydrogen, fluorine or bromine atom) or a group: (in which R^ is defined as above, and and which may be the same or different, each represents 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 alkylsulphonyl group containing from 1 to 4 carbon atoms, a trifluoromethyl group, a 3,4-methylene-dioxy group, or a chloro, fluoro or bromo group, and B" represents an oxygen atom or a sulphur atom) and R represents a saturated or unsaturated, straight, branched or cyclic alkyl radical containing up to 18 carbon atoms, as well as the mixtures of these isomers. The compounds of formula (I') may exist in isomeric forms when they possess one or more centres of asymmetry in the alcohol part. H r 18 17 1 *}*?-; tyer •*- v » j. * t) - 8 - ft' When ^ represents an alkyl radical this is preferably the methyl, ethyl, n-propyl, isopropyl or n-butyl radical. When k represents a benzyl radical substituted by one or more alkyl radicals this is preferably the methyl or ethyl radical(s). ft' When A represents a benzyl radical substituted by one or more alkenyl radicals, this is preferably the vinyl, allyl, 2-methylallyl or isobutenyl radicalCs). J*' When A represents a benzyl radical substituted by one or more alkenyloxy radicals, this is preferably the vinyloxy, allyloxy, 2-methylallyloxy or isobutenyloxy radical(s). When ^ represents a benzyl radical substituted by one or more halogen atoms, this is preferably the chlorine, bromine or fluorine atomKs). When R represents a straight or branched saturated alkyl radical, this is preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, tert-butyl, tert-pentyl or neopentyl radical. When R represents a cyclic radical', this is preferably a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radical, a straight or branched alkyl radical bearing one of these radicals or a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radical substituted by one or more alkyl radical(s) of which the bond with the group - GOO - is situated on any one of its apices, for example the 1-methylcyclobutyl, 1-methylcyclopentyl, 1-methylcyclohexyl or 2,2,3>3-tetra-methylcyclopropyl radical. 1 ^fy i JL-vJ * i 4 O - 9 - When R represents an unsaturated alkyl radical, way be this is an ethylene radical such as, for example, a vinyl or 1, 1-dimethylallyl radical or an acetylene radical such as, for example, the ethynyl or propynyl radical. The subject of the invention is especially, among the compounds of formula (I*), those corresponding to the formula (I): (I) in which the double bond has the geometry z/ A represents: either an alkyl radical containing from 1 to 18 carbon atoms, o pti 10 _or a benzyl radical pooaibl-y substituted as defined before, or a group: CH2R2 in which the substituents R^ and R2 are as defined before, or a group: 1 // ' " ; c l. U -10- in which R^ is as defined before, or a group: in which B^, R1^ and R'2 keep the same meanings as before, or a group: 5 in which B, R^, R^ and n keep the same meanings as before, or a group: h % it. cn or a group: 1 t Jl * ■ «> - 11 - in which the substituents Eg, Er,, Eg, E^ and S/I are defined as before, 10 Among the compounds of the invention there may be mentioned in particular the compounds for which R represents a methyl radical. There may also be mentioned those for - 12 - 1^5 j. c? % x » ^ which R represents an ethyl, n-propyl, isopropyl, tert- butyl or cyclopropylmethyl radical. There may also be mentioned especially the compounds for which A represents a (4-S) 3-methyl-2-(2-propenyl) — l-oxo-cyclopent-2-en-4-yl group. There may also be mentioned the compounds for which A represents a (1,3,4,5,6,7-hexahydro- -l,3~dioxo-2H-isoindol-2-yl)-methyl group, an(HS) cyano— ben z y I (6-phenoxy-2-pyridinyl)"methyl group, a [j[phenylmethyl)-3~ -furanyljmethyl group, a l-(3-propargyl_2,5~dioxo -imidazolidinyl)-methyl group or an (R)^ 3-phenoxyphenyl) — ethyl group. The subject of the invention is especially the compounds of which the preparation is given in the experimental part. Among these compounds of the invention there may be mentioned in particular: - (IS) 2-methyl-4-oxo-3-(2-propenyl)-2-cyclopenten-l-yl (IR cis) 2,2-dimethyl-3C(Z)-3-niethoxy-3-oxo-l-propenyl]cyclo-propane-carboxylate, - l-(3_propargyl-2,5-dioxo-imidazolidinyl)-methyl (IR cis) 2,2-dimethyl-3C(Z)-3"tert-butoxy-3-oxo-l-propenyl]-cyclopropane -carboxylate; .1 - l-(3~propargyl 2,5-dioxo-imidazolidinyl)-methyl (IR cis) 2,2-dimethyl-3C(Z)-2-cyclopropylmethoxycarbonylethenyl] -cyclopropane-carboxylate; - 1(R) 3-phenoxyphenyl-ethyl (IR cis) 2,2-dimethyl-3C(Z)-2-is opropoxyc arbonyl-e thenyl]-eyelopropane—carboxylate; - l-(3-propargyl-2,5-dioxo~imidazolinyl)-methyl (IR cis) 2,2-dimethyl~3C(Z) 2-isopropoxy-carbonyl-ethenyl]-cyclo- 1 Q> 71 f7 5 J. o i _L » ^ - 13 - propane-carboxylate. A further subject of the invention is the compound (RS)<*;-cyano- (3-benzoylphenyl) methyl (1R,cis,£2)2,2-dimethyl-3- (3-m<ihoxy-3-oxo-1 -propenyl) -cyclopropane-1-carboxylate, which is closely related in structure to the compounds of formula (I1) and which falls within the general formula (I') described and claimed in our co-pending Application No. 196809. This compound is denoted herein Compound Y. The compounds of formula (I') and Compound Y show interesting properties which enable them to be used in the control of pests : this can be, for example, the control of pests of plants, domestic pests and pests of warm-blooded animals. Thus the products of the invention can be used to control insects, nematodes and acaridae which are pests of plants and of animals. The subject of the invention is therefore the use of the compounds of formula (I'), as defined before and of Compound Y, in the control of pests of plants, domestic pests and pests of warm-blooded animals. The product of formula (I') and Compound Y can therefore be used especially to control insects in the agricultural sphere, ;to control, for example, aphicfe , the larvae of lepidoptera and coleoptera. They are used at doses between 10 g and 300 g of active substances per hectare. The products of formula (I1) and Compound Y can-also be used to control insects in the domestic sphere, to control especially flies, mosquitoes and cockroaches. Certain of the products of formula (I') show, in particular, excellent knock-down capacity. The product of Example 1 is particularly remarkable. The products of formula (I) are more photostable and 197175 - 14- - are not toxic to mammals. All these properties make products of formula (I1) ctsul. &rr\ JJCCLSI. d V ^products which correspond perfectly to the requirements of the modern agro-chemical industry: they enable the crops to be protected whilst preserving the environment. as\d C6+r\pusid- V The products of formula (I')/caEi also be used to pests control the acaridae and the nematodes which are ftarabileV of plants« Compc+j^td The compounds of formula (I')/can also be used to pas (rS control the acaridae which are yaracitoa* of animals, to control, for example, ticks and especially the ticks of the species Boophilus, those of the species Hyalomnia, those of the species Amblyomnia and those of the species Rhipicephalus, 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 ptsts Jbfce/ compositions jiHtondcdf for the control of ^araoitod of pests pests warm-blooded animals, domestic ftaraoitca and jparaoitofl of plants, characterised in that they contain at least one of the products defined above. j The subject of the invention is especially the insecticidal compositions containing, as active principle, at least one of the products defined above. The subject of the invention is especially the compositions containing as active principle: - (IS) 2-methyl-4-oxo —3~(2-propenyl)-2-cycloper.ten-l-yl (1H c 2,2-dimethyl-3C(Z) 3-methoxy-3-0x0-1-propenylJ-cyclopropane carboxylate; - 15 - - l-(3-propargyl-2,5~dioxo imidazolidinyl)-methyl (IE cis) 2,2-dimethyl-3C(Z) 3-tert-butoxy-3-oxo-l-propenyl]~ cyclopropane-carboxylate; - l-(3-propargyl-2,5-dioxo-imidazolidinyl)-methyl (IR cis) 2,2-dimethyl~3C(Z)-2-cyclopropylmethoxy-carboxylethenyl]~ cyclopropane-carboxylate; - 1(R) 3~phenoxyphenyl~ethyl (IR cis) 2,2-dimethyl~3t(Z) 2-isopropoxycarbonyl-ethenylJ-cyclopropane-carboxylate;ad - l-(3~propargyl^2,5~<iioxo imidazolidinyl)-methyl (IR cis) 2,2-dimethyl-3[(Z) 2-isopropoxycarbonyl-e thenyl]-eyelo-propane-carboxylate and/ , f—1(11) 3~phenogyphenyl ethyl (IR trans)—2,2-diuiblli,yl / ^•"[(g) 2-ibupropoxjiCdirbonyl ethenyl] cyclopropano oarbojiylatoy' The compositions according to the invention are prepared according to the usual processes of the agro-chemical industry, the veterinary industry or the industry of products intended for animal feeding. In these compositions intended for agricultural and domestic use, the active substance or substances can 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 surface-active agent ensuring, in addition, uniform dispersion of the substances constituting the mixture. The vehicle used . . .. _ - 16 - can be a liquid such as water, alcohol, the hydrocarbons or other organic solvents, a mineral,animal or vegetable oil, a powder such as talc, the clays, the silicates or kieselguhr or a combustible solid. 5 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 domestic use, the compositions according to the invention 10 are used in the form of smoke-producing compositions. The compositions according to the invention can then be advantageously constituted, for the non-active part, by a combustible insecticidal coil or else by an incombustible fibrous stibstrate. In the latter case the fumigant obtained 15 after incorporating 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 Machilus Thumbergii leaf powder), 20 pyrethrum-stem powder, cedar-needle powder, wood dust (such as pinewood sawdust), starch and coconut shell powder. The dose of active substance can be, for example, from 0.05 to 1% by weight. 25 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 95% "by weight. ii , . <!' » . - 17 - The compositions according to the invention^for domestic use,can also be obtained by preparing an atomisable oil based upon active principle, this oil soaking the wick of a lamp and being then subjected to 5 combustion. The concentration of the active principle incorporated in the oil is preferably from 0.03 to 95% "by weight. The insecticidal compositions according to the invention, like the acaricidal and nematocidal compositions, 10 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 acaricidal use preferably wettable powders for 15 foliar spraying are used containing from 1 to ,80% or liquids for foliar spraying containing from 1 to $00 g/1 of active principle. Powders for foliar spraying can also be used containing from 0.05 to 3% of active substance. For nematocidal use preferably liquids for soil 20 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. 25 In order to increase the biological activity of the products of the invention, they may be added to standard synergists used in a similar case such as l-(2,5»8-trioxa- 197175 - 18 - dodecyl) 2-propyl 4-, 5-methylenedioxy 1361126116 (or piperonyl butoxide) or N-(2-ethyl heptyl) bicyclo[2,2-l]-5~heptene- -2,3-d.i carboximide, or piperonyl-bis-2-(2'-n-butoxy ethoxy) ethylacetal (or tropltal). When it is a question of controlling the acaridae pests 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 to the animal species: it can contain cereals, sugars and grains; soya bean-} peanut- and sunflower-cake; meals of animal origin, for example fish meals; synthetic amino acids, mineral salts, vitamins and antioxidants. The subject of the invention is, therefore, the feeding compositions defined above. O^pex^icL Y The compounds of formula (I'^show excellent general tolerance, and the subject of the invention is, therefore, ctsiM of y also the products of formula (I')yas 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 in human medicine to control lice, by way of prevention or cure, and to control scabies. They can also be used as anthelmintics. The medicaments according to the inventionaan be administered by external route, by vaporisation, by bath a fS i®--' > *?. - - <&r , f - 19 - or by painting on. The medicaments according to 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 previously. It may also be pointed out that the products of the invention can be used as biocides or as growth regulants. The subject of the invention is also /aooooia-* compositions feions—endowed/ with insecticidal, acaricidal or nematocidal activity, characterised in that they contain as active substance on the one hand one at least or Ccmpcusid V of the compounds of general formula (I'^and on the other hand one at least of the pyrethrinoid esters selected from the group constituted by the esters of ^.llcthrolonofe, of 3,^-,5-6-tetrahydrophthalimido-methyl alcohol, of 5-benzyl-3-furyl-methyl alcohol, of J-phenoxy-benzyl alcohol alcohol . with and of a-cyano-3-phenoxy-benzyl frlooholai fcrf chrysanthemic acid , by the ester of "5-benzyl~3-furyl-methyl alcohol erf 2,2-dimethyl-3-(2-oxo_3-tetrahydrothiophenylidene - o-Cvcl methyl)-cyclopropane-l-carboxylic feci els, by the esters of 3-phenoxy-benzyl alcohol and of cx-cyano-3-phenoxy-benzyl cUcofvjf i/Afh j2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane- ot ict -1-carboxylic (srcid-3, by the ester, of a-cyano 3-phenoxy cxlicrhoi benzyl fe-3reahaltf e£ 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclo- ¥ k i a - 20 - actci propane- 1-carboxylic by the ester of 3-phenoxy U/utA benzyl alcohol &£ 2-parachlorophenyl-2-isopropyl-acetic aUethrol cmc acids, and by the esters of frllothrolonod, of 3 >4,5*6--tetrahydrophthalimidomethyl alcohol, of 5~t>enzyl 3~furyl 5 methyl alcohol, of 3-phenoxy benzyl alcohol and of a-cyano alcohol 3-phenoxy benzyl fcl-ooholG off 2,2-dimethyl- 3-(l,2,2,2- -tetrahalo)-cyclopropane-1-carboxylic acids, in which "halo" represents a fluorine, chlorine or bromine atom, it being understood that the compounds I' can exist in 10 Mil thsi/ possible stereoisomeric forms like the acid moiebcs and alcohol oopulae of the pyrethrinoid esters above. cub o we Cc*r> pascb orts The froGociationq according to the invention are of especial interest either in enabling a more extensive range of parasites to be combatted by the polyvalence 15 of their activity, 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): (II) O^ci &C c^dopropcis* moiety « f It, c/> stru^Ju*, in which the double bond has the geometry being defined as before, or a functional derivative of this tea ctzcl acid is Subjected with an alcohol of formula (III): A'-OH (III) in which A' keeps the same meaning as before and the corresponding compound of formula (I') is thus obtained. The acid functional derivative used is preferably an acid chloride. The esterification reaction can be carried out according to other processes. It is possible, for example, to react the acid of formula (II) with the alcohol of formula (III) in the presence of dicyclohexylcarbodiimide or of diisopropylcarbodiimide. The compounds of formula (II) are new chemical products of which examples of preparation are given further on in the experimental part. The compounds of formula (II) can be prepared by ui_ a process according which a compound of formula: the Cc/clopromcnetj & I c'-£ strucJu/%, in which/Hal represents a halogen atom and alk represents i a *y i ty e *JL- 6 J, |r tj - 22 - an alkyl radical containing from 1 to 20 carbon atoms, is reacted firstly with an alkali agent capable of taking away the halogen atoms and secondly either with an agent capable of introducing the carboxylic group to obtain the compound of formula (V): ho2c=c C02alk (v) ^ UJ4\ICJ\ the cycloprDpct-sie moieh-f ^ which is subjected to the action of an esterif ication agent, to obtain the compound of formula: R02C-CsQ C02alk the CAjoloptvpctsut if>Ot€bj to !R/Ct.s Strx^^jbucSCr in which^R keeps the same meaning as before, or with an alkyl chloroformate of formula: r 0 :-o-?- ci (vi) (v) in which R keeps the previous meaning, to obtain directly • « the compound of formula (VI)| N.Z. PATENT office 14 MAR 1984 197175 - 23 - then the compound of formula (VI) is subjected to the action of a hydrogenation agent, to obtain the compound of formula: CC^alk (VII) douALc Utncl ha* ** georfccy -Z Mcl fa ujc/opnpcw nwtty » i W,a± Sfiucfust in which th^feroup CQ^R is at position Z, which is subjected to the action of an acid hydrolysis agent capable of cleaving selectively the branched ester function on the carbon at 1, to obtain the corresponding compound of formula (II): (II) The subject of the invention is also a process for XO preparing the compounds of formula (I1), characterised in that a compound of formula. (VIII): ho2c CO^' (VIII) 1 f)71 ^ - - the ctjcloproposed moiety >o ^ iR/ds Sbructi*-TE a-nci in which^A' is defined as before is subjected to the action of an esterification agent, to obtain the corresponding compound of formula (I'). The subject of the invention is also a process as defined before, characterised in that the compound of formula (VIII) is prepared by subjecting a compound of formula (IX): ci5c-ch2-o2c-csc (12) uAucJ\ tto Cycleprt>pa+VL moietrij k> <=/ IR,cis strucJxtsX-Ito the action of an alcohol of formula (III): a' - oh (III) in which a1 is defined as before, to obtain the compound 10 of formula (2): C15C-CH2-02C-C£C (2) v) tkt ctjcAopr&pcc^si moiety to ^ IR, c<s /which is subjected to the action of an agent for cleaving the ester function borne by the acetylene carbon, to obtain the compound of formula (XI): cc\f> n I) -X l\ 1 0'~-< ?7Cr O5 « JL » o - 25 - HZC CH, 3 \ ✓ * H02C-CsC C02A' (21) agent to obtain the compound of formula (VIII). In a preferred method of carrying out the above process of the invention: 5 - the esterification of the compound (IX) takes place by reacting the compound (12) with the alcohol (III), in the presence of dicyclohexyl carbodiimide or of diisopropyl carbodiimide; - the cleavage of the ester (2) takes place by using a 10 metal powder, for example zinc powder, in acidic medium; and presence of a catalyst such as palladium, in the presence of traces of quinoline. The process above contains an obvious variation 15 according to which the stages of hydrogenation and of esterification are reversed. The subject of the invention is, therefore, also a process as defined above, characterised in that a compound of formula (XI): the ftarcfu3/ hydrogenation agent is hydrogen in the - 26 - 10 H02 C-CSC (XI) :«/ tfje cucloprtpc^w moiety » °j IR, cis stru.Uu^ a^, in which/A' is defined as before, is subjected to the action of an esterification agent, to obtain the compound of formula (XII): h,c ch- eo2 c-c=c (XII) fc/te cujciop p moiztij u> <jj MZt ots sCrucht-fZ. in which^R and a* are defined as before, which is subjected to the action of a ^rtTfirr 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. -'The compound of formula (IX) can be prepared by subjecting an acid of formula (XIII): l': h02 c-c=c C02 alk (XIII) -i <? i 1 *' O - 27 - cqoloprcrpccsa Mcnety » / cor SOzsotus? in which^alk represents an alkyl radical containing from 1 to 18 carbon atoms, to the action of 2,2,2-trichloro- ethanol then by subjecting the ester obtained to acid hydrolysis. An example of preparing a compound of formula 12 is described hereinafter in the experimental portion. The intermediate products obtained which carrying out the process of the invention are new chemical products and the subject of the invention is, therefore, also as new industrial products and especially as intermediate products necessary for carrying out the invention, the products of formulae (VIII), [(X) ,j (21) and (XII). The alcohols of formula III used in the process of the invention are generally know products. Horvever,—buine ul Uifcssti aleohola;—that io to 3Qy fehe producfea of formula / CVAOH in which and Rj / are defined as herein before, are new chemical products and allow to obtain esters particularly . remarkable from a/biologic point of view. * / The subjeciy of the invention is also these alcohols as new industrial /prodicts and especially as intermediate products necessary for/carrying out the invention. Among tQese alcohols, there may be mentioned, in particular ,—tha /3-phonoxy 4—fluoro ^(-mcthyl-bengylic alcohol. . These alcohols can be prepared as indicated fterc in aftei^ in the experimental position, by reaction of an ^fgano metallic lV '7s 28 product, for example, a methyl-magnesium halide, with the aldehydes corresponding to the desired alcohols. Compound Y may be prepared by methods analogdiis to those described above for the preparation of compounds of formula (I') using corresponding intermediates in which R is replaced by an (RS)-a-cyano-(3-benzoylphenyl)methyl group. The following examples illustrate the invention without, however, limiting it. oP\ - .26 - 1 O *y sr Example 1: (IS) 2-methyl-4--oxo 5-(2-propen:yl)-2-c;yclo- penten-l-.yl (IR cis, AZ) 2,2-dimethyl-5C5-inethoxy-5-oxo-l- -propenyl]cyclopropane carboxylate. Stage A: (l_RJ.ci>s_1_ AZj_ 2_,dimeth2l_3£^^me_th°xy_3~oxo ^-£ropen2lJ.c^cl^o£ropan.£ _carb£X2;li:c_a£id ^hloilide^ o 3 At 0 C, 1 cur of thionyl chloride is introduced into a mixture containing 1.8 g of (IR cis,AZ) 2,2-dimethyl 3C2-methoxy 3~oxo 1-propenyll cyclopropane carboxylic acid, prepared as indicated hereinafter in preparation 1, and ■z 10 cur of isoprene. The whole is maintained under agitation for 30 minutes at 0°C, then at 20°C for 4- hours. It is concentrated to dryness under reduced pressure at 50°C. A product is obtained which is used as it is in the following stage. Sta.ge_ B: Xl^_2-m£thyl-4~o.x°. j~_(2~propenyj.)^2-c;^clp£enten^. zlzJJk IAIi c.is.,_AZ )_2,2-dimethyl-3Cj-methoxy-3-oxo- 1-propenyl3 cy2.1£p.r oj> ane_caxbo xy^ate^ 761 mg of (4S)-hydroxy 3-methyl 2-(2-propenyl) 2-cyclopenten-l-one, 5 benzene and 0.4 cm^ of pyridine are mixed. The solution is cooled to 10°C and 888 g of (IR cis, AZ) 2,2-dimethyl 3t3-methoxy 3^oxo-l--propenyl3 cyclopropane carboxylic acid chloride in solution in 9 cnr of benzene, are added. The reaction mixture is maintained under agitation for 16 hours. It is poured into water and the organic phase is decanted and washed with water. It is dried, filtered and brought to dryness. 1.9 g of a product are obtained and chromatographed on ■■ . 30 197175 silica, eluant benzene / ethyl acetate (95=5)• 1.06 g of the product sought are thus obtained. [<x3d - +71°5 - 2°5 (c = 0.5% CHClj). NMB : CDQI-t in p.p.m. 1.3 and 1.32 hydrogen of the methyls at 2, 1.9 - 2.05 H at 1 of the cyclopropane, 3.1 - 3-3 ~ 3«4 H at 3 of the cyclopropane, 6.5 to 6.8 H of the carbon at 1 of the ethenyl radical, 5.8 - 6.04 H of the carbon at 2 of the ethenyl radical, 3-7 H of the methoxy group, 5.6 to 5-8 H ofthe carbon at 4 of the (4S) 3-methyl 1-oxo cyclopent-2-en-4-yl radical, 2.95 to 3 H of the carbon at 1 of the propenyl radical, 5.5 to 6.2 H of the carbon at 2 of the propenyl radical, 4.8 to 5-2 H of the carbon at 3 of the propenyl radical. Example 2: (IS) 2-methyl-4-oxo-3-(2-propenyl) 2-cyclopenten--1-yl (IB cis, A2) 2,2-dimethyl 3~(3-ethoxy-3-oxo-l-propenyl) cyclopropane carboxylate. 1 g of dicyclohexylcarbodiimide, 6 mg of 4-dimethyl amino pyridine and 12 cm^ of methylene chloride are introduced into a round flask containing 1.1 g of (IB cis, AZ) 2,2-dimethyl 3~(3-ethoxy 3-0x0 1-propenyl) cyclopropane carboxylic acid, prepared as indicated hereinafter in preparation 2. 900 mg of (4S) 4-hydroxy 3-methyl 2-(2-propenyl 2-cyclopenten-l-one, in solution in 1 cnr of methylene chloride, are then added. The reaction mixture is maintained under agitation for 16 hours. It is filtered 1 oty-'i it JL -J .• j, / u and the filtrate is concentrated to dryness under reduced pressure and 2.4 g of a product are thus obtained which is purified by chromatography on silica: eluant: n-hexane / isopropyl ether (6:4). 1.3 g of the product sought are obtained. [a]|j ■ +34° - 2° (c = 0.6% in benzene). NKR: CDCl^ in p.p.m. 1.27 H of the methyls at 2, 3.1 to 3.4 H of the carbon at 3 of the cyclopropane, 6.4 to 6.8 H of the carbon at 1 of the ethenyl radical, 5.8- 6 H of the carbon at 2 of the ethenyl radical, 1.17, 1.28, 1,4 and 4 to 4.4 H of the ethoxy group, 4.7 to 5.2 H of the carbon at 3 of the propenyl radical. Example 3: (IS) 2-methyl-4-oxo-3-(2-propenyl) 2-cyclopenten--1-yl (IS cis, AZ) 2,2-dimethyl-3(3-oxo-3-propoxy-l-propenyl) cyclopropane carboxylate. Work being carried out as in Example 2, starting with 1.5 g of (IR cis, AZ) 2,2-dimethyl 3-(3-oxo-3-propoxy--1-propenyl) cyclopropane carboxylic acid and l.lg of (4S) 4~hydroxy 3"inethyl 2-(2-propenyl) 2-cyclopenten-l-one, 3.1 g of the product sought are obtained and purified by chromatography on silica, eluant: hexane /isopropyl ether (7:3)° It is brought to dryness and 1.7 g of the product sought are obtained. ' • [a]D = +39°5 " 2°5 (c = 0.5% in benzene), UHR : CDCl^ in p.p.m. 1.3 and 1.31 H of the methyl at 2 of the cyclopropane, 197175 '' ' £- 3-1 to 3.42 H borne by the carbon at 3 of the cyclopropane, 6.4 to 6.8 H of the carbon at 1 of the ethenyl radical, 5.8 - 6 H of the carbon at 2 of the ethenyl radical, 4 - 4.08 - 4.2 H of the' propoxy radical at a of the COgi 5 0.83 - 0.95 - 1.06 H of the propoxy radical at y of the CO2, 5-6 to 5.7 H of the carbon at 4 of the (4S) 3-methyl 2-(2-propenyl) 1-oxo cyclopent 2-en-4-yl radical^ 2 H of the methyl at 3. of the (4S) 3-methyl 2-(2-propenyl) 1-oxo cyclopent-2-en-4-yl radical, 10 4.7 to 5.2 H of the carbon at 3 of the propenyl radical. Example 4: (IS) 2-methyl-4-oxo 3-(2-propenyl) 2-cyclopenten--1-yl (IR cis, AZ) 2,2-dimethyl 3-C3-(l-methylethoxy)-3--oxo-l-propenyl] cyclopropane carboxylate. Stapie A: £lR £i^,_AZ)_2^2^drm_ethyl 3z.li.lz.m^^J"l.e_thox^)_ 15 ^-ox£-l_-£ropenjl_]_ eye 1 op_ro£.ane_c arb oa.c_id_eh 1 o_rid«. A mixture of 900 mg of (IR cis, AZ) 2,2-dimethyl 3-C3--(1-methyl-ethoxy) 3-oxo-l-propenyl]cyclopropane carboxylic acid, 9 cm^ of isoprene and 1 cm^ of thionyl chloride is agitated for 4 hours at ambient temperature. It is brought 20 to dryness and 1.4 g of a product are obtained which is used as it is in the following stage. .Stage. B: (1S2 2_-meth2l-4^oxo^3z(.E~£r2P.£nZl). cyclopenten-l-yl OLR c_is,_AZ )_2JL2^d^methyl <^-_[3z.(l~®ei^Zl_e^°.:xZ)_3z02£0 l-jDropenjlJ^ cy^l^pj? ojd ane_c^rb o xj3at e.. * containing 25 1.5 cur of pyridine are added to a mixture / 1.4 g of the x product prepared in Stage A, 10 enr of benzene and 750 mg of (4S) 4-hydroxy 3-methyl 2-(2-propenyl) cyclopent-2-en-l-one. N.Z. PATEMT OFFICE 14 MAR 1984 RECEIVED 1 071' * i * JL * -X- The reaction mixture is maintained, under agitation for 3 hours and poured into a mixture of iced water and 2N hydrochloric acid (100 cm^ and 20 cm^). The aqueous suspension is extracted with ethyl acetate. The organic phases are washed with water until neutral, dried and filtered and the filtrate is concentrated to dryness under reduced pressure. 2.3 g of a product are obtained which is chromatographed on silica, eluant: cyclohexane / ethyl acetate (8:2). 486 mg of the product sought are thus obtained. [a]jj = +26° - 2° (c = 0.3% in benzene). NMR : CDCl^ in p.p.m. 1.28 and 1.32 H of the methyls at 2 of the cyclopropane, 1.88 - 2 H of the carbon at 1 of the cyclopropane, 3-11 to 3.4 H of the carbon at 3 of the cyclopropane, 6.4 to 6.8 H of the carbon at 1 of the ethenyl radical, 5.8 - 6 H of the carbon at 2 of the ethenyl radical, 5 H of the carbon of the isopropyl at a of the C = 0, 1.3 H of the carbons of the isopropyl at 3 of the CO, 4.8 to 5-2 H of the carbon at 3 of the propenyl radical, 5-7 H of the carbon at 4 of the (4S) 3-methyl 2-(2-propenyl) 1-oxo cyclopent-2-en-4-yl radical, 2 H of the carbon at 3 of the ,(4S) 3-methyl 2-(2-propenyl) 1-oxo cyclopent-2-en-4-yl radical. Example 5' (RS) cyano (6-phenoxy"-2-pyridinyl) methyl (IR cis, AZ) 2,2-dimethyl 3-(3-methoxy-3-oxo-l-propenyl) cyclopropane carboxylate. 4.96 g of (IR cis, AZ) 2,2-dimethyl 3-(3-methoxy 3-0x0 -bk - 32 i r\ 4 e ~ o i X V tj 10 15 20 1-propenyl) cyclopropane carboxylic acid are introduced z z into 75 cur of methylene chloride. 2 cur of pyridine are then added, then 5.2 g of dicyclohexylfcarbodiimide. The whole is agitated for a few minutes and 5-9 S of (RS) a-hydroxy 6-phenoxy-2-pyridine acetonitrile are introduced, then 0.1 g of 4-dimethylaminopyridine. The reaction mixture is maintained for 1 hour under agitation, then it is filtered. The filtrate is concentrated under reduced pressure. The residue is chromatographed on a column, eluant: cyclohexane /ethyl acetate (85:15). 7-7 g of the product sought are thus obtained. [<x]D = +59° 1 2.5° (c = 0.5% CHClj) NMR : CDCl^ in p.p.m. 6.3 H borne by the carbon bearing the CTT group, 1.22 - 1.27 and 1.3 H of the methyls at 2 of the cyclopropane, 3.17 to 3-5 H of the carbon at 3 of the cyclopropane, 3.7 H of the methoxy group. 5.8 to 6.0 ethylenic E at a of the carboxyl, 6.3 to 6.6 ethylenic H at (3 of the carboxyl, 6.9 - 7 H borne by the carbons at 3 and 5 of the pyridine, 7.7 - 7-8 - 7.9 H borne by the carbon at 4 of the pyridine. Example 6: (1, 3<4, 5«6,7-hexahydro 1,3-dioxo-2H-isoindol-»2-yl) methyl (IR cis, AZ) 2,2-dimethyl 5[3-methoxy 5-oxo-1--propenyl] cyclopropane carboxylate. Work being carried out as in Example 1, Stage B, starting with 1.5 g of (IR cis, AZ) 2,2-dimethyl C-3-methoxy carbonyl ethenyl] cyclopropane carboxylic acid chloride 35 - 5% - 1 Q7l >7" * J, * o and 1.4 g of l,3,4,5,6,7-hexahydro-2-hydroxymethyl -1H--isoindole-l,3_(2H) dione, 3 S of a product are obtained and chromatographed on silica, eluant: cyclohexane / ethyl acetate (8:2). It is "brought to dryness and 1.86 g of the 5 product sought are obtained. NME : CDCl^ in p.p.m. 1.27 and 1.3 H of the methyls at 2 of the cyclopropane, 1.78 - 1.93 H borne by the carbon at 1 of the cyclopropane, 3.06 - 3.53 H borne by the carbon at 3 of the cyclopropane, 10 5.8 - 6 ( (H borne by the carbon at 2 of the ethenyl radical, 6.4 to 6.8( 3.7 H of the methyl of the methoxy radical, 1.6 to 2 H of the carbons 4,5>6 and 7 of the indole, 5.5 H of the methylene at a of the CO2 bonded to the carbon at 15 1 of the cyclopropane. Example 7? [5-(phenylmethyl)-3-furanyl] methyl (IB. cis, AZ) 2,2-dimethyl-3(5~methoxy-3-oxo-1-propenyl) cyclopropane " carboxylate. Work being carried out as in Example 1, starting 20 with 3.22 g of (IE cis, AZ) 2,2-dimethyl 3[3~methoxy-3-oxo--1-prbpenyl] cyclopropane carboxylic acid chloride and 2.8 g of 5""(phenylmethyl]-3-furanyl methanol, 6.3 g of a product are obtained which is chromatographed on silica: eluant: cyclohexane / ethyl acetate (8:2). 2.33 g of 25 the product sought are thus obtained. Ca]D = +48° ± 1°5 (c = 0.7% CHClj) NKR CDCl^ in p.p.m. iZ 1 o 71 n x - 29 - O i i / o 1.26 - 1.28 H of the methyls at 2 of the cyclopropane, 1.86 - 2.02 H of the carbon at 1 of the cyclopropane, 3.0 to 3-3 H of the carbon at 3 of the cyclopropane, 6.4 to 6.8 H of the carbon at 1 of the ethenyl radical, 5-8 - 5-9 H of the carbon at 2 of the ethenyl radical, 3.7 H of the methoxy group, 4.9 H of the CH2 group at a of the CO bonded to the carbon at 1 of the cyclopropane group, 7.3 H of the carbon at 2 of the furanyl radical, 6 H of the carbon at 4 of the furanyl radical, 7.2 aromatic H's. Example 8; [l-(2-propenyl)2,4-dioxo imidazolidin-5-yl] methyl (lR,cis,AZ) 2,2-dimethyl 5-(3-propoxy-5-oxo-l--Dropenyl) cyclopropane carboxylate. 1.2 g of (IE cis, AZ) 2,2-dimethyl 3~(3~propoxy-3-0x0- -1-propenyl) cyclopropane carboxylic acid, 20 cm^ of * methylene chloride and 100 cnr of 4-dimethyl amino, pyridine are mixed. 1 g of dicyclohexylcarbodiimide is then introduced into the solution thus obtained. 900 mg of 3-hydroxymethyl-l-(2-propynyl)-2,4-imidazolidinedione are then introduced, under agitation. The reaction mixture .is agitated for 16 hours at 20°C and filtered. The filtrate is washed with N hydrochloric acid, then with water until neutral, dried and brought to dryness under reduced pressure. An oil is obtained which is chromatographed on silica, eluant: benzene / ethyl acetate (8:2). 1.2 g of the product sought are obtained. - 1 <#>") 197175 - -90 - [a]^ = +2° - 1° (c = 0.5% in "benzene). NKR CDC1, in p.p.m. 1.25 and. 1.28 H of the methyls at 2, 1.83 - 1-97 H of the carbon at 1 of the cyclopropane, 5 3.0 to 3-4- H of the carbon at 3 of the cyclopropane, 6.4 tp 6.7 H of the carbon at 1 of the ethenyl radical, 5.6 - 5-8 H of the carbon at 2 of the ethenyl radical, 4 - 4.1 - 4.2 H of the propoxy at a of the C=0, 0.83 - 0.95 ~ 1-07 H of the propoxy at a of the 0=0, 10 2.33 - 2.37 - 2.41 H of the carbon at 3 of the propynyl radical, 4 H of the carbon at 3 of the 2,5~dioxoimidazolidinyl radical, 4.2 - 4.3 H of the methylene at a of the triple bond. - 2rT- 1Q717- -i i J. t U Example 9: Metaphenoxy benzyl (IR cis, Az) 2,2-dimethyl 3~(3-oxo 3-methoxy-l-propenyl) cyclopropane-1-carboxylate. Into 20 cm^ of methylene chloride are introduced 2 g of (IR cis, Az) 2,2-dimethyl 3~(3*-oxo 3-methoxy-l-propenyl) 5 cyclopropane-l-carboxylic acid, 0.9 cnr of pyridine and 2.5 g of dicyclohexylcarbodiimide, the whole is agitated for 10 minutes, 2.4 g of metaphenoxy benzyl alcohol are added, the whole is agitated for 1 hour 30 minutes, 40 mg of dimethylaminopyridine are added, the whole is agitated 10 for 2 hours 30 minutes, the insoluble matter formed is eliminated by filtration, the filtrate is concentrated to dryness under reduced pressure, the residue is chromatographed on silica eluting with a cyclohexane / ethyl acetate mixture, 9:1, and 3 g of metaphenoxy benzyl (IR cis, Az) 2,2-dimethyl 15 3~(3-oxo 3-niethoxy-l-propenyl) cyclopropane-1-carboxylate are obtained. /a/ •+48° - 1*^° (c " ^ chloroform) Analysis : ^2^20? 5 (380.444) C% H% f— 20 Calculated 72-51 6.36 / '4 MAS Mi Found 72-7 6.4 In a manner similar to that described in Example 9, starting with the appropriate-Bcids and alcohols, the following compounds were prep'ared: 25 Example 10; a (RS) cyano [3(4-bromophenoxy) phenyl] methyl (IR cis, Az) 2,2-dimethyl 5-(3~methoxy 3-oxo-1-propenyl) cyclopropane-l-carboxylate. 7f\ - 3# - 1Q71 Analysis : (C^H^rNO^) (484.342) C% H% Br N% calculated 59-51 4-58 16-50 2.89 found 59-7 4.6 16.2 2.8 NKR Spectrum (CDCl^) - Peaks from 1.26 to 1-34 p.p.m., attributed to the hydrogens of' the geminal methyls. - Peaks at 1.97 - 2.06 and from 3.22 to 3-48 p.p.m., attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. - Peaks at 3-7 - 3-73 p.p.m., attributed to the hySrcgerisof C0~- - Peaks at 5-85 ~ 5-98 and 5-9 ~ 6-05 p.p.m., attributed ^ to the ethylenic hydrogens (ester side chain). - Peak at 6.33 p.p.m., attributed to the hydrogen of -CH-CN. - Peaks from 6.43 to 6.67 p.p.m., attributed to the ethylenic hydrogens (cyclopropyl side chain). - Peaks from 6.85 to 7.52 p.p.m., attributed to the hydrogens of the bromophenyl. - Peaks from 6.94 to 7-55 p.p.m., attributed to the hydrogens of the other aromatic nucleus. Example 11: 4-oxo 4 (H) pyran 3-yl (IB cis, Az) 2,2- -dimethyl 3-(3-methoxy 5-oxo 1-propenyl) cyclopropane-1- -carboxylate. M.Pt. = 106°C. /a/jj : +153° ~ 2-5° (c = 0-8%, benzene). Example 12: 1 (R) (3-phenoxyphenyl) ethyl (IR cis, Az) 2,2-dimethyl 3-(3-isopropoxy 3-oxo 1-propenyl) cyclopropane- -1-carboxylate. /a/jj : +140° - 2-5° (c = 1%, benzene) MT OFFir.P UO - - 197175 Example 13: 1 (R) (3-phenoxyphenyl) ethyl (IB cis, Az) 2,2-dimethyl-3-(3-ethoxy 3-oxo 1-propenyl) cyclopropane--1-carboxylate. /a/p : +145° - 2-5° (c = 1%, benzene). Example 14: 1 (R) (3-phenoxyphenyl) ethyl (IB cis, Az) 2,2-dimethyl 3(3-methoxy 3-oxo 1-propenyl) cyclopropane-1--carboxylate. /a/p : +130.5° - 2.5° (c = 1%, chloroform). Example 15: (RS) g-cyano (3-benzoylphenyl) methyl (IR cis Az) 2,2-dimethyl 3-(3-methoxy 3-oxo 1-propenyl) cyclo- propane-l-carboxylate. /a/jj : +43° - 1° (c ax 1%, toluene). Example 16: (3-benzoylphenyl) methyl '(IR cis, Az) 2,2-dimethyl 5 (3-methoxy 3-oxo 1-propenyl) cyclopropane-1-carboxylate. /a/D : +520 - 1.5° (c = 1%, chloroform). Example 17: (2, 3» 4, 5* 6 pentafluorophenyl) methyl (IR cis, Az) 2,2-dimethyl 3 (3-methoxy 3-oxo 1-propenyl eyelopropame-1-carboxylate. /cc/p : +29.5° - 2° (c = 0.8%, chloroform). Example 18: (RS) cyano (2, 3^ 4, 5^ 6 pentafluorophenyl) methyl (IR cis, Az) 2,2-dimethyl 3 (3-methoxy 3-oxo 1-propenyl) cyclopropane-1-carboxylate. Analysis : °18H14I,5N04 (40 C% H% Wo F% calculated 53-61 3-50 3.47 23.55 found 53.9 3.5 3.4 23.7 U\ 1 071 7tr Example 19: (RS) cyano 2-(6-phenoxy pyridyl) methyl (IP. cis, Az) 2,2-dimethyl-5 C3-oxo 3~n -propoxy l-propenyl3 eye lopropane-1- c arboxyl at e. /a/D : +55° i 2.5° (c » 0.5%, chloroform). 5 Example 20: IR (3-phenoxyphenyl) ethyl (IB cis Az) 2,2-dimethyl 3 (3~propoxy 3-oxo 1-propenyl) eyelopropane-1--carboxylate. /a/p : +123° - 2° (c = 0.9%, chloroform). Example 21: 1 (B) (3-phenoxyphenyl) 2-propyn-l-yl (IB cis, 10 Az) 2,2-dimethyl 3~(3-methoxy 3~oxo 1-propenyl cyclopropane--1-carboxylate. /a/^ : +55-5° ~ 1-5° (c = 1%, chloroform). Example 22: 1 (B) (3-phenoxyphenyl) 2-propyn-l-yl (IR cis, Az) 2,2-dimethyl 3 (3-isopropoxy 3-oxo 1-propenyl) cyclo-15 propane-l-c arboxyl ate. M.'Pt. = 66°C. /a/D : +47° - 1° (c = 1.2%, chloroform). Example 23: IB (3-phenoxyphenyl) 2-propyn-l-yl (IB cis, Az) 2,2-dimethyl 3(3-n-propoxy 3-oxo 1-propenyl) cyclopropane--1-carboxylate. 20 /a/n : +48° " 2° (c a 1%, chloroform). Example 24: (4-benzoyl phenyl) methyl (IB cis, Az) 2,2-dimethyl 3(3-methoxy 3~oxo 1-propenyl) cyclopropane-l-carboxylate. /a/D : +46° + 2° (c = 1%, chloroform). Example 25: (RS) cyano 2-(6-phenoxy pyridyl) methyl (IR cis 25 Az) 2,2-dimethyl 3-C3-oxo 3-terttutoxy l-propenyl3 cyclo- N.Z. PATENT /a/D : +68° - 1.5° (c = 1%, chloroform). received 1*2- 1 0*7-1 *■?* J-U i I i (J Example 26: (RS) cyano (4-benzoylphenyl) methyl (IR cis, Az) 2,2-dimethyl 3(5-methoxy 3-oxo 1-propenyl) eyelopropane-1--carboxylate. Analysis : 5^ (417.466) ■ C% H% , N% calculated 71.93 5-85 3-35 found 71.9 5.8 3-2 Ex am-pie 27: (5-propyn-2-yl 2,5-dioxoimidazolidinyl) methyl (IR cis, Az) 2,2-dimethyl 3-[3-oxo 5-tertbutoxy 1-propenyl] cyclopropane-l-carboxylate. /a/D : +31° - 2° (c » 0.5%, chloroform). Example 28: (3-propyn 2-yl 2,5-dioxoimidazolidinyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-isopropoxy 3-oxo 1-propenyl) cyclopropane -1-carboxylate. M.Pt. = 78°C. /a/D : +15.5° ~ 1° (c = 1%, chloroform). Example 29: (3-propyn 2-yl 2,5-dioxoimidazolidinyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-cyclobutoxy 3-oxo 1-propenyl) cyclopropane-l-carboxylate. /a/p : +18° - 1° (c = 1.2% chloroform). Example 30: (3-propyn 2-yl 2,5-dioxoimidazolidinyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-isobutoxy 3-oxo 1-propenyl) cyclopropane-l-carboxylate.^ /a/p : +20.5° " 1«5° (c = 1%» chloroform). Example 31: (3~propyn-2 yl 2,5-dioxoimidazolidinyl) methyl (IR cis, Az) 2,2-dimethyl 3 C3-oxo 3~ethoxy 1-propenyl] cyclopropane-l-carboxylate. /a/D : +10° - 4° (c = 0.2%, chloroform). N.Z. PATENT nppmp l\b 1 7 «. -j- -i* * JL * t> Example 32; 1 (R) C3-phenoxyphenyl) 2-propyn-l-yl ClR cis, Az) 2,2-dimethyl 5 C3-ethoxy 3-oxo 1-propenyl eyclopropane--1-carboxylate. /a/p : +48.5° - 2° (cEbroform). 5 Example 33: [5 benzyl 3-furyl] methyl (IR cis, Az) 2,2--dimethyl 3-[3-oxo 3-isopropoxy 1-propenyl] cyclopropane--l-'carboxylate. /a/^ : +44° +2° (c = 0.4%, chloroform). Example 34: Metaphenoxy benzyl (IR cis, Az) 2,2-dimethyl 10 3[3-oxo 3-iBopropoxypropenyl] cyclopropane-l-carboxylate. /a/D : +42° - 2° (c = 0.5%, chloroform). Example 35:(RS) cyano 2-(6-phenoxy pyridyl) methyl ClR cis, Az) 2,2-dimethyl 3-[3-oxo 3(cyclopropyl methoxy) propenyl] cyclopropane-l-carboxylate. 15 /a/D : +53° 1 2° (c = 0.5%, chloroform). Example 36: (5-benzyl 3-furyl) methyl ClR cis, Az) 2,2--dimethyl 3[3-oxo 3-n-propoxy propenyl] eyelopropane-1--carboxylate. /a/jj : +41° - 2° (c = 0.5%> chloroform). 20 Example 37: 1, 3* 4, 5^ 6, 7~hexahydro 1,3-dioxo 2 H isoindol-2-yl) methyl ClR cis, Az) 2,2-dimethyl-3 [3-oxo 3-isopropoxy propenyl] cyclopropane-l-carboxylate. M.Pt. = 94°C. /a/D : -22.5° - 2° Cc = 0.5%, chloroform). 25 Example 38: (1, 3, 4, 5« 6, 7-hexahydro 1,3-dioxo 2H isoindol-2 yl) methyl ClR cis, Az) 2,2-dimethyl 3[3-oxo 3-n propoxy 1-propenyl] cyclopropane-l-carboxylate. M.Pt. = 76°C. r— N-Z. PATENT OFRCB umRim'-'-: 1971 ri * rrr e -L »' O /a/jj : -15° (c = 0.15%, carbon tetrachloride). Example 39: Metaphenoxy benzylClR cis, Az) 2,2-dimethyl 3(3-oxo 3'n-propoxy 1-propenyl) cyclopropane 1-carboxylate. /a/D : +40° - 2° (c - 0.5%, chloroform). Example 40: Metaphenoxy benzyl (IR cis, Az) 5C5-oxo 3-cyclopropyl methoxy) 1-propenyl] cyclopropane-l-carboxylate, /a/p : +46.5° - 2° (c = 0.6%, chloroform). Example 41: 1 (R) (3~phenoxyphenyl) ethyl (IR cis, Az) 2,2-dimethyl 3(3~cyclobutoxy 3-oxo 1-propenyl) cyclopropane- -1-carboxylate. /a/p : +125.5° - 2° (c = 1%, chloroform). Example 42: [1, 3* 4, 5^ 6, 7-hexahydro 1,3-dioxo 2H isoindol 2-yl] methyl (IR cis, Az) 2,2-dimethyl 3 [3-oxo 3-(cyclopropyl methoxy) 1-propenyl] cyclopropane-l-carboxylate. M.Pt. : 102°C. /a/p : +6.5° - 2° (c =0.3%, chloroform) Example 43: (5-benzyl 3-furyl) methyl (IR cis, Az) 2,2- -dimethyl 3-[3-oxo 3-(cyclopropyl methoxy) 1-propenyl] cyclopropane-l-carboxylate. /a/D : +42° - 2° (c = 0.7%, chloroform). Example 44: (S) 2-methyl 4-oxo 3-(2-propenyl) 2-cyclopentenyl (lRcis, Az) 2,2-dimethyl 3-[3~oxo 3(cyclopropyl methoxy) 1-propenyl] cyclopropane-l-carboxylate. /a/D : +64.5° - 2.5° (c = 1%, chloroform). Example 45: (3-propyn-2-yl 2,5-dioxoimidazolidinyl) methyl (IR cis, Az) 2,2-dimethyl 3 [3~cyclopentyloxy 3-oxo 1-propenyl] eyelopropane-1-c arboxylate. patent office U MARI984 44" 1 u. « 2 t U /a/p : +15.5° - 1*5° (c = 1%, chloroform). Example 46: (BS) cyano 2-(6-phenoxy-6-pyridinyl) methyl (IE cis, Az) 2,2-dimethyl 3-[3-oxo 3-cyclopentyloxy 1-propenyl] cyclopropane-1-carboxylate. /a/jj : +42° - 1° (c = 0.9%, benzene). Example 47:(3~propyn-2 yl 2,5-dioxoimidazolidinyl) methyl (IE cis,Az) 2,2-dimethyl 5(5-methoxy 3-oxo 1-propenyl) cyclopropane 1-carboxylate. /a/jj : ~ +1° (c = 0.5%, benzene). Example 48: (5-propyn 2-yl 2,5-dioxoimidazolidinyl) methyl (IE cis, Az) 2,2-dimethyl 3 [3-sec-butoxy 3-oxo 1-propenyl] cyclopropane-1-carboxylate. /a/p : +16.5° - 1° (c = 0.8%, chloroform). Example 49: (S) cyano 3-phenoxy 4-fluorophenyl methyl (IE cis, Az) 2,2-dimethyl 3[3-methoxy 3~oxo 1-propenyl] cyclopropane-1-c arboxylate. /a/D : +56.5° - 2.5° (c = 0.5%, benzene). Example 50:: (B,S) 1-(4-fluoro-3-phenoxyphenyl) 2-propyn 1-yl (IE cis, Az) 2,2-dimethyl 3[3-methoxy-3-oxo-1-propenylJ cyclopropane-1-c arboxyiate. NMB Spectrum (CDCl^) - Peaks from 1.22 to 1.32 p.p.m., attributed to the hydrogens of the geminal methyls. - Peaks at 1.09 - 2.05 and from 3«lto 3.43 p.p.m., attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. - Peaks from 2.62 to 2.66 p.p.m., attributed to the hydrogen of the = CH. f-i^cSfVss 1 Qfy-i n~s _A. K/ i * <J - Peaks at 3.72 - 3*73 p.p.m., attributed to the hydrogens of the CC^-CH^. - Peaks from 5*8 to 6 p.p.m., attributed to the ethylenic hydrogen (ester side chain). 5 - Peaks from 6.38 to 6.83 p.p.®., attributed to the ethylenic hydrogen (cyclopropyl-side chain) and to the hydrogen of the CO -CH0. 2 \ 2 - Peaks from 6.9 to 7.55 p.p.m., attributed to the hydrogens of the aromatic nuclei. 10 Example 51: (bs) l(4-fluoro-3-phenoxyphenyl) 2-propyn 1-yl (IB cis, Az) 2,2-dimethyl 3[5(l,l-dimethyl-ethoxy)-5-oxo-l--propenyl] cyclopropane-l-carboxylate. NMB Spectrum (CDCl^) - Peaks from 1.22 to 1.31 p.p.ia., attributed to the hydrogens 15 of the geminal methyls. - Peaks at 1.47 - 1.5 p.p.m., attributed to the hydrogens of the tertbutyl. - Peaks at 1.87 ~ 2.01 and from 3-12 to 3-43 p.p.m., attributed to the hydrogens at positions 1 and 3 of the 20 cyclopropyl. - Peaks from 2.6 to 2.65 p.p.m., attributed to the hydrogen of the = CH. - Peaks at 5«7 ~ 5-9 p.p.m., attributed to the ethylenic hydrogen (ester side chain). 25 - Peaks from 6.28 to 6.72 p.p.m., attributed to the ethylenic hydrogen (cyclopropyl side chain) and.to the hydrogen of the CO^-CH. 14 MAR 1984 -4 un AG ■i ri *1 * r~->r 1d i ± io oo 2; on c o uu > LU O LU CE - Peaks from 6.91 to 7»55 p.p.m., attributed to the hydrogens of the aromatic nuclei. Example 52: (R,S) l-(6-phenoxy-2-pyridinyl) 2-propyn 1-yl (IR cis, Az) 2,2-dimethyl 3(3-methoxy-3-oxo-1-propenyl) 5 eyelopropane-1-c arboxylat e. IOTIR Spectrum (CDCl^) - Peaks from 1.23 to 1.31 p.p.m., attributed to the hydrogens of the geminal methyls. - Peaks at 1.96 - 2.1 and from 3-13 to 3-4? p.p.m., 10 attributed to the hydrogens at positiors 1 and 3 of the cyclopropyl. - Peaks from 2.59 to 2.63 p.p.m., attributed to the hydrogen of the = CH. - Peak at 3«73 p.p.m., attributed to the hydrogens of C02CH^. 15 - Peaks from 5-78 to 6.02 p.p.m., attributed to the ethylenic hydrogen (ester side chain). - Peaks at 6.3 - 6.34- p.p.m., attributed to the hydrogen of the CO2-CH. - Peaks from 6.43 to 6.88 p.p.m., attributed to the ethylenic 20 hydrogen (cyclopropyl side chain). - Peaks from 6.75 to 7*9 p.p.m., attributed to the hydrogens of the aromatic nuclei. Example 53• (R,S) l-(6-phenoxy 2-pyridinyl) 2-propyn-l-yl (IR cis, Az) 2,2-dimethyl 3C3-(l^l-dimethyl ethoxy) 3-oxo 1-propenyl] cyclopropane-l-carboxylate. MR Spectrum (CDCl^) - Peaks from 1.24 to 1.32 p.p.m., attributed to the hydrogens i O ^ i »7 ~ of the geminal methyls. - Peak at 1.$ p.p.m., attributed to the hydrogens of tertbutyl. - Peaks at 1.93 ~ 2.07 and from 3-13 to 3.46 p^p.m., 5 attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. - Peaks from 2.59 to 2.63 p.p.m., attributed to the hydrogen of the = CH. - Peaks from 5.68 to 5-90 p.p.m., attributed to the 10 ethylenic hydrogen (ester side chain). - Peaks at 6.3 - 6.34 p.p.m., attributed to the hydrogen of C0o-CH q . 2 | 2 - Peaks from 6.47 to 6.86 p.p.m., attributed to the ethylenic hydrogen (cyclopropyl side chain). 15 - Peaks from 6.75 to 7-9 p.p.m., attributed to the hydrogens of the aromatic nuclei. Example 54: Phenyl methyl (IR cis, Az) 2,2-dimethyl 5-C5--(1,1-dimethyl ethoxy) 3-oxo l-pronenyl] cyclopropane-1--carboxylate. 20 NMR Spectrum (CDCl^) - Peaks from 1.28 to 1.32 p.p.m., attributed to the hydrogens of the geminal methyls. - Peak at 1.5 p.p*m., attributed to the hydrogens of the tertbutyl. 25 - Peaks at 1.9 - 2.04 and from 3.08 to 3-41 p.p.m., attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. NXiY»y"\T{>rF!CB. Vv^ A& 197175 - Peak at 5-15 p.p.m., attributed to the hydrogens of CO2 — CHg — ^. - Peaks at 5*72 - 5-92 p.p.m., attributed to the ethylenic hydrogen (ester side chain). 5 - Peaks from 6.38 to 6.75 p.p.m., attributed to the ethylenic hydrogen (cyclopropyl side chain). - Peak at 7-4 p.p.m., attributed to the hydrogens of the aromatic nucleus. Example 55: (6-phenoxy 2-pyridinyl) methyl (IE cis. Az) 10 2,2-dimethyl 3-[3-(l-l-dimethyl ethoxy) 3-oxo 1-propenyl] cyclopropane-l-carboxylate. NHE Spectrum (CDCl^) - Peaks at 1.3 - 1.32 p.p.m., attributed to the hydrogens of the geminal methyls. 15 - Peak at 1.51 p.p.m., attributed to the hydrogens of the tertbutyl. - Peaks at 1.96 - 2.11 and from 3«13 to 3-47 p.p.m., attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. 20 - Peak at 5«13 p.p.m., attributed to the hydrogens of co2-ch2-. - Peaks at 5-73 - 5-92 p.p^m., attributed to the ethylenic hydrogen (ester side chain). - Peaks from 6.37 to 6.73 p.p.m., attributed to the ethylenic 25 hydrogen (cyclopropyl side chain). - Peaks at 7.58 - 7»72 - 7-85 p.p.m., attributed to the hydrogens of the pyridyl nucleus. N.Z. PATC: :"tfXPFlCH 14 MAR 1984 :V 4 ' 5 10 15 20 at n^-5 ~ o i -L * <J Example 56: (6-phenoxy-2-pyridinyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-methoxy-3-oxo-1-propenyl) cyclopropane-1--carboxylate. NMR Spectrum-(CDCl^) - Peak at 1.3 p.p.m., attributed to the hydrogens of the geminal methyls. - Peaks at 1.98 - 2.13 and from 3-13 to 3.4-5 p.p.m., attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. - Peak at 3-74 p.p.m., attributed to the hydrogens of co2-CH5. - Peak at 5-12 p.p.m., attributed to the hydrogens of CO2-CH2-. - Peaks at 5-82 - 6.02 and from 6.5 to 6.87 p.p.m., attributed to the ethylenic hydrogens. - Peaks from 7 to 7.85 p.p.m., attributed to the hydrogens of the aromatic nuclei. Example 57: (R,S) l-(6-phenoxy 2-pyridinyl) ethyl (IR cis, Az) 2,2-dimethyl 3C3-(l,l-dimethyl ethoxy) 3-oxo 1-propenyl] cyclopropane-l-carboxylate. NMR Spectrum (CDCl^) - Peaks from 1.25 to 1.32 p.p.m., attributed to the hydrogens of the geminal methyls. - Peaks at 1.47 - 1.57 p.p.m., attributed to the hydrogens of C0o-CH-. - Peak at 1.5 p.p.m., attributed to the hydrogens of the tertbutyl. V sv ,&■<r 1 o *y i n - Peaks at 1.95 - 2.09 and from 3.12 to 3.4-3 p.p.m. attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. - Peaks from 5*63 "fco 5-97 p.p.m., attributed to the 5 hydrogen of CO2-CH2 . - Peaks from 5.67 to 5.92 and from 6.32 to 6.75 p.p.m., attributed to the ethylenic hydrogens. - Peaks from 6.67 to 7«5 p.p.m., attributed to the hydrogens of the aromatic nuclei. 10 - Peaks from 7«55 to 7«83 p.p.m., attributed to the hydrogens of the pyridyl nucleus. Example 58: (R,S) l-(6-phenoxy 2-pyridinyl) ethyl (IR cis, Az) 2,2-dimethyl 3-(3-methoxy-3-oxo-1-propenyl) cyclopropane--1-carboxylate. 15 MIR Spectrum (CDCl^) -•Peaks from 1.25 to 1.3 p.p.m., attributed to the hydrogens of the geminal methyls. - Peaks from 1.43 to 1.57 p.p.m., attributed to the hydrogens of the CO2-CK- 20 ^3 - Peaks at 1.97 - 2.11 and from 3»1 to 3.4-2 p.p.m., attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. - Peaks from 5-63 to 6.08 p.p.m., attributed to the hydrogen 25 of CO2-CH2 . - Peaks from 5-78 to 6.02 and from 6.45 to 6.87 p.p.m., attributed to the ethylenic hydrogens. N.Z. PATENT OFFICE 14 MAR 1984 RECEIVED <o± 5>L u. u < 1 t d - Peaks from 6.67 to 6.8 and from 7 to 7-67 p.p.m., attributed to the hydrogens of the aromatic nuclei. - Peaks from 7-55 to 7-83 p.p.m., attributed to the hydrogens of the pyridyl. 5 Example 59: [3-(phenyl carbonyl) phenyl] methyl (IE cis, Az) 2,2-dimethyl 3C3-(l->l~dimethyl ethoxy) 3~oxo 1-propenyl] eyelopropane-1-c arboxylate. Analysis : 0,2^-^^ (434.537) C% H% 10 calculated 74.63 6.96 found 74.60 7-00 Example 60: IB (3-phenoxyphenyl) 2-propyn-l-yl (IB cis, Az) 2,2-dimethyl 3(3-tertbutoxy 3-oxo 1-propenyl cyclopropane-l-carboxylate . 15 : +58° - 1.5° (c = 1.2%, chloroform). Example 61: (IB (3-pkenoxyphenyl) ethyl (IB cis, Az) 2,2-dimethyl 3-(3-cyclopropyl methoxy 3-oxo 1-propenyl) cyclopropane carboxylate. /a/p : +121° - 3° (c = 0.6%, chloroform). 20 Example 62: (3-propyn 2-yl 2,5-dioxoimidazolidinyl) methyl (IB cis, Az) 2,2-dimethyl 3~(5-cyclopropyl methoxy 3-oxo 1-propenyl) cyclopropane carboxylate. /a/jj : +14° - 2° (c = 0.5%, chloroform). Example 63: (IB) (3-phenoxyphenyl) 2-propyn-l-yl (IB cis, 25 Az) 2,2-dimethyl 3-(3-cyclopropyl methoxy 3-oxo 1-propenyl) cyclopropane carboxylate. /a/D : +46° - 2° (c = 0.5%, chloroform). I— ■&> $2 O i JL * <J Example 64: (3-propyn-2-yl 2,5-dioxoimidazolidinyl) methyl (IB cis, Az) 2,2-dimethyl 3-(3-n-butoxy 3-oxo 1-propenyl) ■ cyclopropane carboxylate. /a/D : +17° - 1° (c = 1%, chloroform). 5 Example 65: (S) cyano (3-phenoxy 4-fluorophenyl) methyl (IB cis, Az) 2,2-dimethyl 5-(5-ethoxy 5-oxo 1-propenyl) cyclopropane carboxylate. /a/p : +47.5° - 2° (c = 0.5%i chloroform). Example 66: (S) cyano (3-phenoxy 4-fluorophenyl) methyl 10 (IB cis, Az) 2,2-dimethyl 5-(3-isopropoxy 3-oxo 1-propenyl) cyclopropane carboxylate. /a/D : +50° - 2° (c = 0.3%* chloroform). Example 67: (S) cyano (3-phenoxy 4-fluorophenyl) methyl (IB "cis, Az) 2,2-dimethyl 3-(3-cyclopropyl methoxy 3-oxo 15 1-propenyl) cyclopropane carboxylate. /a/D : +53° (c « 0.25%, chloroform). Example 68: (2, 3* 4, 5< 6-pentafluorophenyl) methyl (IB cis, Az) 2,2-dimethyl 3~(3-tertbutoxy 3-oxo 1-propenyl) cyclopropane carboxylate. 20 /a/D : +37.5° - 1-5° (c = 1%, chloroform). Example 69: (3-phenoxy 4-fLuorophenyl) methyl (IB cis, Az) 2,2-dimethyl 3-(3-tertbutoxy 3-oxo 1-propenyl) cyclopropane carboxylate. /a/jj : +55-5° - 2.5 (c = 0.5%» chloroform). 25 Example 70:(3-pbenoxy 4-fluorophenyl) methyl (IB cis, Az) 2,2-dimethyl 3~(3-methoxy 3-0x0 1-propenyl) cyclopropane carboxylate. NtSi OFFICE 14 MAR 1984 ■f fyf t jl . u /(x/D : +50.5° 1 2.5° (c -0.75%, chloroform). Example 71: (1 RS) (3-phenoxy 4-fluorophenyl) ethyl (IR cis, Az) 2,2-dimethyl 3-(3-tertfrutoxy 3-oxo 1-propenyl) cyclopropane carboxylate. MIR Spectrum (CDCl^) - Peaks from 1.19 to 1.28 p.p.m., attributed to the hydrogens of the geminal methyls. - Peaks at 1.48 - 1.5 p.p.m., attributed to the hydrogens-of the tertbutyl. - Peaks from 1.41 to 1.53 p.p.m., attributed to the hydrogens of the C0~-CH— - Peaks at 1.85 - 1.99 and from 3.07 to 3.38 p.p.m., attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. - Peaks from 5*58 to 6 and from 6.27 to 6.7 p.p.m., attributed to the ethylenic hydrogens. - Peaks from 6.27 to 6.7 p.p.m., attributed to the hydrogen of C0o-CHo . 2 i 2 - Peaks from 6.92 to 7.53 p.p.m., attributed to the hydrogens of the aromatic nuclei. Example 72: (1 RS) (3-phenoxy 4-fluorophenyl) ethyl (IR cis, Az) 2,2-dimethyl 3-(3-methoxy 3-oxo 1-propenyl) cyclopropane carboxylate. " " NMR Spectrum (CDCl^) - Peaks from 1.19 to 1.29 p.p.m., attributed to the hydrogens of the geminal methyls. - Peaks from 1.41 to 1.54 p.p.m., attributed to the hydrogens of the C0-.-CH-2 | ch3 5<3 _1 j j. . O -Peaks at 1.87 - 2.02 and from 3'07 to 3.22 p.p.m., attributed to the hydrogens at positions 1 and 3 of the cyclopropyl. - Peaks from 5-82 to 6.17 p.p.m., attributed to the hydrogen 5 of C02-CH2 . - Peaks from 5«93 to 6.2 and. from 6.58 to 7 p.p.m., attributed to the ethylenic hydrogens. - Peaks from 7.03 to 7.72 p.p.m., attributed to the hydrogens of the aromatic nuclei. 10 Example 73: 5-benzyl 3-furyl methyl (IR cis, Az) 2,2-dimethyl 3-(3-tertbutoxy 3-oxo 1-propenyl) cyclopropane carboxylate. /a/D : +54-.50 1 1.5° (c -■!%,. chloroform). Example 74: (IS) 2-methyl 4-oxo 3 (2-propenyl) cyclopenten--1-yl (IR cis, Az) 2,2-dimethyl 3-(3-tertbutoxy 3-oxo 15 (1-propenyl) cyclopropane carboxylate. /a/D : +73° (c = 0.25%, chloroform). Example 75:(2-phenoxy 5-thiazolyl) methyl (IR cis, Az) 2,2-—dimethyl 3~ (3-methoxy 3-oxo 1-propenyl) cyclopropane carboxylate. M.Pt. = 62°C. 20 /a/u : +60.5° - 1.5° (c «= 1.5%•, benzene). Example 76: (RS) thioamido phenoxyphenyl methyl (IR cis, Az) 2,2-dimethyl 3~(3-methoxy 3-0x0 1-propenyl) cyclopropane carboxylate. IR Spectrum: 25 - Absorptions at 1632 cm"^ (C = C) 3475 - 336c —'"1 <=£> >&■ 197175 EOTR Spectrum (deuterochloroform) - Peaks at 1.25 - 1.27 - 1.30 p.p.m., attributed to the hydrogens of the geminal methyls. - Peaks at 1.97 - 2.11 p.p.m., attributed to the hydrogen 5 at position 1 of the cyclopropyl. - Peaks at 3.08 - 3.4-3 p.p.m., attributed to the hydrogen at position 3 of the cyclopropyl. - Peaks at 3.69 - 3«72 p.p.m., attributed to the hydrogens of the methyl of the methoxy carbonyl. 10 - Peaks at 5.73 - 5»92 p.p.m. and 5.8 - 5.99 p.p.m., attributed to the ethylenic hydrogen at a of the C02-CH^. - Peaks at 6.32 - 6.66 p.p.m., attributed to the ethylenic hydrogen at 1 of the -C^-CH^. - Peak at 6.4-2 p.p.m., attributed to the hydrogen bonded 15 to the carbon bearing the group -C-NH. S Example 77: (2-phenoxy 5-thiazolyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-tertbutoxy 3-0x0 1-propenyl) cyclopropane carboxylate. /a/D : +68° - 1.5° (c = 1%, chloroform). 20 Example 78: (RS) cyano (2-phenoxy 5-thiazolyl) methyl (lR.cis, Az) 2,2-dimethyl 3~(3-methoxy 3-oxo 1-propenyl) . cyclopropane carboxylate. /a/p : +60° - 2° (c s 1^, chloroform). Example 79: (RS) cyano (2-phenoxy 5-thiazolyl) methyl (IR cis, 25 Az) 2,2-dimethyl 3~(3-tertbutoxy 3-oxo 1-propenyl) cyclopropane carboxylate. /a./-* : +65° - 2° (c = 0.5%, chloroform). Example^^l: 1 (R) (3-^phenoxyphenyl) ethyl ClR cis, Az) 2,2-dimethyl 3l3-allyloxy 3-oxo 1-propenyl] cyclopropane carboxylate. Stage A: Tertbutyl _£_1R £i^)_2^2-dime_thyl ^( j5trichl£ro-_ £thoxy_^oxo^£opynyl)_cZcio£ropan£ £a£b£x~£l a.t£:_ 6.2 g of dicyclohexylcarbodiimide are introduced into a solution containing 7-15 S of tertbutyl (IR cis) 2,2-dimethyl 3(3-bydroxy 3~oxo propynyl) cyclopropane carboxylate, prepared as was indicated in preparation 2A, and 80 mg of •z dimethylamino pyridine in 35 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 one hour and the precipitate formed is eliminated 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 of an oil J are obtained which is chromatographed on silica eluting with the benzene / ethyl acetate mixture (97:3)• 9 g of the product sought, melting at 70-71°C, are thus isolated. Stage B: (lR_ci_s_)_ 2,2-dimetlr^l 5_(L3_a_5zPc_hloroethoxy^. 2.32.°x°_JP£OjDynyl)_c^c Iojd ropane £a^b£X2;li c_a£i d : A mixture containing 11.4 g of the product prepared •% w 00 0 CV, 1 « ! DC < £'! O T ! ' : • c i $% •4 f \ t~ A *+. r~ i' i i i o according to Stage A, 120 cm^ of toluene and 300 mg of . paratoluenesulphonic acid is taken to reflux for one hour. It is allowed to return to ambient temperature, and the reaction mixture is washed with water, it is dried and 5 it is brought to dryness. 9«5 g of the product sought are thus obtained, which is used as it is in the following stage. Stage C_:_ _1 R ^^henoxy^h^n^l}, ethyl X.1.2 _cis)_2_12^dimethyl richlor£ethax^ J5-£X£ jDrop^n^l^ cyclopropane ^ 10 carboxylate. 5 6 g of the product obtained according to Stage B, 30cm • of methylene chloride and 600 mg of 4-dimethylaminopyridine are mixed. 3«95 g of dicyclohexylcarbodiimide are then introduced 15 into the solution thus obtained, slowly at 0°C, under agitation, the whole is agitated again for 30 minutes, still at 0°C, then drop by drop, at the same temperature, a solutioh of 4.1 g of 1(R) (3-pbenoxyphenyl) ethanol in 12 cm^ of methylene chloride is added. 20 The reaction mixture is agitated for 17 hours at ambient temperature and filtered. The filtrate is brought to dryness under reduced pressure. An oil is obtained which is chromatographed on silica, eluant cyclohexane / ethyl acetate (8:2). 4.4 g of the product sought are 25 obtained. Stage, D: iE_Q-^h^nop?2phenyl)_e_thJjl__(lR_ci.s}_ 2^dimethyl _3(3~hydr£X2; 3-ox£ £rop^jl—cxcj-o^ropane c_arb£x^late_. s°\ $ ^ 1C.^i r -JL. O i JL * tj 0.53 g of powdered zinc is introduced, under agitation, into a solution of 4.16 g of the product prepared in Stage C in 4 cm^ of methylene chloride and 45 cm^ of acetic acid. The whole is agitated for 30 minutes at ambient temperature 5 then again 0.53 g of powdered zinc is added. This operation is repeated twice more then the residual zinc is eliminated * 2 by filtration and rinsed with 40 cnr of water and 100 cur of methylene chloride. The filtrate is extracted with methylene chloride. It is washed, dried and brought to 10 dryness under reduced pressure. 3-05 g of the product sought are thus obtained. _Stage_ E: 1. 3;ipheno^ry^he.n;z;l^_ ethyl _£lR cis., &z)_ 2,2- ^dimethyl hydroxy J-oxo 1-propenyl] cye I opr op311 e_ ^arbox^l^t^. 15 Hydrogenation of 3 6 of the product prepared in the previous stage in 80 cm^ of ethyl acetate is carried out in the presence of 500 mg of 10% palladium hydroxide on 7. barium sulphate and 0.9 cur of quinolme. The product is filtered and the filtrate is washed with hydrochloric acid 20 then with water. It is dried and brought to dryness under reduced pressure. 2.9 g of the product sought are thus 1 obtained. Stage F: 1 (IQ_ £3;^benoxy£h£n^l) ethyl .£12* cis. »_Az) 2,^-di^ejfchjl^X^z.allZ1®.3^ 2.~2.XSL i~£ropenjl]_ eyelopr op ane_ cs: 1 s?-j £g25...:! ^axbjoxjl ate. 'I .♦ i* 1.4 g of 1 (R) (3-phenoxyphenyl) ethyl (IR cis.Az) }• ' 2,2-dimethyl 3C3-hydroxy 3~oxo 1-propenyl] cyclopropane to 5^ i O1 JL U1 carboxylate (prepared in Stage E), 7 cm^ of methylene chloride and 0.14 g of 4-dimethylaminopyridine are mixed. 760 mg of dicyclohexylcarbodiimide are introduced at 0°C under agitation, the whole is agitated again for 20 minutes o 3 at 0 C then at this same temperature 0.26 cur of allyl * alcohol m 2 cnr of methylene chloride is added. The reaction mixture is agitated for one hour at ambient temperature, then filtered. The filtrate is brought to dryness under reduced pressure and an oil is obtained which is chromatographed on silica, eluant: hexane / isopropyl ether (8:2). 570 mg of the product sought are obtained. /a/^ : +109.5° ~ (c = 1%, chloroform). Example S3&: 1 (5) (3-phenoxyphenyl) ethyl (15 cis, Az) 2,2-dimethyl 3C3~tertbutoxy 3-oxo 1-propenyl] cyclopropane carboxylate. 1.4 g of o-tertbutyl N,N'-diisopropyl urea is introduced, under agitation at ambient temperature, into a solution of 1.74 g of 1 (5) (3-phenoxyphenyl) ethyl (15 cis, Az) 2,2-dimethyl 3E3-bydroxy 3~oxo 1-propenyl] cyclopropane carboxylate (prepared according to the' process described in 10 Stage E of Example -81) in 8 cnr of e'thyl acetate. The .r whole is agitated again for 4 hours, then filtered. The filtrate is brought to dryness under reduced pressure. The product obtained is chromatographed on silica, eluant: hexane / ether (8:2). 930 mg of the product sought, melting at 80°C, are thus obtained. /oc/p : +125° ~ 2° (c = 1%, chloroform). 1 q fir -i' V » J* H %J Example #3: Metaphenoxy benzyl (IR cis, Aa) 2,2-dimethyl 3 (3~tertbutoxy 3~oxo 1-propenyl) cyclopropane carboxylate. Stage A: Me_ta^henoxj_ benzj£l_(l_R_cis}_ _2,2-dimethjl_3-C2»-2».2r ~tric_hlo_roethoxy 5-oxo_propynyl)__c£cl opropane £a rb£X2l a. t e.. 6.7 g of (IR, cis) 2,2-dimethyl 3(3,3,3~trichloroethoxy 3-oxo propynyl) cyclopropane carboxylic acid (prepared so , according to Stage B of Example j8i), 67 cnr of methylene chloride and 200 mg of 4-dimethylaminopyridine are mixed. Then at 0°C and under agitation, 4.5 g of metaphenoxybenzyl x alcohol in 5 car of methylene chloride are introduced, then 5 a solution of 4.4 g of dicyclohexylcarbodiimide in 5 cm of methylene chloride. The reaction mixture is ag±ated for 3 hours at ambient temperature and filtered. The filtrate is brought to dryness under reduced pressure and 11.5 g of an oil are obtained which is chromatographed on silica, eluant: cyclohexane / ethyl acetate (85:15)- 7-1 g of the product sought are obtained. .Stage B: Me_tajohen^xj £enzj2l_(2J3_cis.)_ 2,2-dimejth2l_3-(J5-_ hydroxy ir£xo .grop^njl^ cy£l£pro£ane_carboxylate^ 5 g of powdered zinc are introduced, under ag±ation, into a solution of 5 g of the product prepared in Stage A with 18 cm^ of acetic acid and 2 cm^ of water. The whole is agitated for 2 hours at ambient temperature, then the residual zinc is eliminated by filtration and rinsed with water, then with methylene chloride. The organic phase is washed with water, dried and brought to dryness under reduced pressure. The residue obtained is taken up with <o% ft , 1.07175 toluene and brought to dryness Tinder reduced pressure. This latter operation is repeated 3 times. 3-6 g of product are thus obtained which is used as it is for the following stage Stage C_: Met^ajohenoxj ben(JL B_c is^ 2,2-dime_th2l_3-(^*"_ ^tjirjfcbutaxj |-oxo _£rop^nxlJ. cy^lop^o^ane^carboxylat^e^ Drop by drop, under agitation at ambient temperature, 3 4 cnr of o-tertbutyl N,N'-diisopropylurea are introduced into 2 g of the product obtained in the previous stage. 25 car of ethyl acetate are then added and the whole is / agitated for one hour. The excess reagent is destroyed by the addition of 2 cm^ of acetic acid and the remainder is agitated again for 15 minutes. It is filtered and rinsed with ethyl acetate and the filtrate is brought to dryness. 2.8 g of an oil are obtained which is purified by chromatography on silica, eluant: cyclohexane / ethyl acetate (8:2). 1.4 g of the product sought are thus obtained. Stage D: Met_ajDh enoxj; benz2;l_(_lx?_ci>s_L Az^ 2,2-dimeth^l 3. JL^Z^rtbutox^ 3-oxo JL-£r op en;£L]_ cj£lop£0£ane_carboxy3.at_e_1_ Hydrogenation of 1.4 g of the product prepared in the 3 previous stage in 30 cnr of ethyl acetate is carried out in the presence of 500 mg of 10% palladium hydroxide on barium sulphate and 0.7 cm^ of quinoline. The product is filtered and the filtrate is washed with 2N hydrochloric acid and with water, dried and brought to dryness under reduced pressure. An oil is thus obtained which is purified twice by chromatography on silica, eluant: cyclohexane / ethyl acetate (ist time 9:1) (2nd time 95:5). 6$' O '"V ST ^ i i » 1 g of the product sought is thus obtained. /a/-Q : +38.5° ~ 2.5° (c = 0.5%, benzene). S3 Example 8A-: (R,S) cyano 2-(6-phenoxy pyridyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-oxo 3-ethoxy 1-propenyl) cyclopropane carboxylate. Stage A.: _£lR £is^)—2^2-dimethyl j-j^3-oxo _3-methoxy_propyrtyl)_ j^cl£P.ro£ane_jcarboxylic cLcid^ A solution containing 2.6 g of tertbutyl (IR cis) 2,2-dimethyl 3-(3~oxo 3-methoxy propynyl) cyclopropane carboxylate, prepared according to Stage A of preparation 1, 25 cnr of toluene and 100 mg of paratoluene sulphonic acid is taken to reflux for 1 hour 30 minutes. The whole is allowed to return to ambient temperature and the reaction mixture is maintained under agiation for 20 hours then concentrated to dryness under reduced pressure. 1.95 S the product sought are recovered. Stage B: _£RS)_2-(6-_Dh_en£X2Pj2ri^Zl^. meJtirj 1_(lR_c is 2. 2,2-^dimethyl (3-oxo _3-methoyy_propynyl). cyclopropane £a rb ox^r late. A solution of 19.9 g of (RS) cyano 2-(6-phenoxypyridyl) methanol in 75 cnr of methylene chloride is mixed, , under .* agitation and under an atmosphere of nitrogen, with a solution of 21.6 g of (IR cis) 2,2-dimethyl 3-(3-oxo 3--methoxypropynyl) cyclopropane carboxylic acid (prepared according to the previous stage) in 75 cm^ of methylene chloride. 1 g of 4-dimethylaminopyridine is then introduced at 5°0 then, after dissolution, 21 g of dicyclohexylcarbodiimide. 1 Qf-M rr The whole is agitated for 4 hours at ambient temperature. It is filtered and the filtrate is.concentrated under reduced pressure at 40°C. The residue obtained is chromatographed on silica, eluant: cyclohexane /ethyl 5 acetate (7:3)- 35«4 g of the ester sought are thus obtained. .Stage C: _^RS)_cjano__2-(6-£_hen£X2Jijridj2l). meth2l_(i^_cisl. 2^, 2-dimejth^l_3^(^.-£X£ hydroxyprogyny 1) _cjyc_l°£r_opane £a rb£X2l at e_. 10 A mixture of 35*4 S of the product obtained in the previous stage, of;175 of didxan, of 35 cnr of water and of 5 s of paratoluenesulphonic acid is taken to reflux for 24 hours. The solution is concentrated under reduced x pressure and the residue is taken up with 250 cnr of 15 methylene chloride and 100 car of water. The organic phase is washed with water, dried and concentrated under reduced pressure. The resultant product is chromatographed on silica, cyclohexane / ethyl acetate (6:4) containing 0.1% of acetic acid and 17-7 E of the product sought are thus 20 obtained. Stage. D:_ (RS)_ cyan£ 2-jj62phenoxy£yridyl)_methyl_ _£lR £is_,_ AzjT 2,2 - dime thyl 3 C^-oxo^^-hydro^^l-propenyl ] _c jc 1.0£r£pan£ £arb£X2l£t£. Hydrogenation of 17*7 g of product obtained in the 25 previous stage m 200 cnr of ethyl acetate is carried out -in the presence of 2.5 g of 10% palladium hydroxide on barium sulphate /and -2.5 cnr^ of quinoline at a temperature I r\, —, _ " "r* i n "> • • - /•«» Tf . . '' j T I ^ 107175 of 20°C. The product is filtered and dried, the solvent is evaporated under reduced pressure and the remainder is chromatographed on silica, eluant: cyclohexane / ethyl acetate / acetic acid (6:4:0.1). 15 g of the product 5 sought are thus obtained. Stage E: (RS). cyano. ^-^^heno^cyDyrid-yl)BeiilZl_(iLB_cj.s_:L AzJ_ 2_, 2-dimeth£l_3z ( J5-oxo ho xy_l:ipj: o jd enyl)_cj2cl oZ. I propane^ £a£b ox^rl a t_e. 70 mg of 4-dimethylaminopyridine then 1.13 g of 10 dicyclohexylcarbodiimide are introduced, under agitation and under an atmosphere of nitrogen, into a solution, cooled to 0°C, of 1.95 S of (RS) cyano 2-(6-phenoxypyridyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-oxo 3-bydroxy 1-propenyl) cyclopropane carboxylate (prepared as in the 15 previous stage) in 10 cm^ of methylene chloride and 2 cm^ of ethanol. The whole is agitated again for 1 hour 30 minutes at ambient temperature, filtered and rinsed, the insoluble matter is washed with methylene chloride and the filtrate is concentrated under reduced pressure. The 20 residue is chromatographed twice on silica, eluant: cyclohexane / ethyl acetate (8:2) the 1st time, and (85:15) ,the 2nd time, and 1.4 g of the product sought are thus obtained. 'd ^ '-'i./a/rv : +48° - 2° (c = 0.5%, chloroform). 25 iEx ample j§-5: (RS) cyano 2-(6-phenoxy pyridyl) methyl (IR cis. Az) 2,2-dimethyl 3-C3~oxo 3-isopropyloxy-1-propenyl] cyclopropane carboxylate, S3 Work being carried out as in Example starting with 1.95 S of (RS) cyano 2-(6-phenoxypyridyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-oxo 3~bydroxy 1-propenyl) cyclopropane carboxylate prepared as indicated in Stage D of Example iW, and 2 cnr of isopropanol, an oil is obtained which is chromatographed on silica, eluant: cyclohexane / ethyl acetate (9:1). 1.7 g of the product sought are thus obtained. /a/D : +53° - 2° (c « 0.75%, chloroform). cyano Example &6>: (RS)/2-(6-phenoxypyridyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-oxo 5-cyclobutoxy 1-pro-oenyl) cyclopropane carboxylate. Work being carried out as in Example starting with 2.1 g of (RS) cyano 2-(6-phenoxypyridyl) methyl (IR cis, Az) 2,2-dimethyl 3-[3-0x0 3-hydroxy 1-propenyl] cyclopropane carboxylate, prepared as indicated in Stage D of ^3 -z Example 84, and 1 cnr of cyclobutanol, an oil is obtained which is chromatographed on silica, eluant: hexane / ethyl acetate (8:2). 1.6 g of the product sought are thus obtained. /aA, : +44.5° - 2° (c = 0.5%, benzene). Example 87:(RS) cyano 2-(6-phenoxypyridyl) methyl (IR cis, Az) 2,2-dimethyl 3~(3-oxo 3-n-butoxy 1-propenyl) cyclo-propane carboxylate. S3 Work being carried out as in Example-84, starting with 2.1 g of (RS) cyano 2-(6-phenoxypyridyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3~oxo 3~bydroxy 1-propenyl) cyclopropane carboxylate, prepared as indicated in Stage D of 1 66 197175 3 Example and 1 cnr of n-butanol, an oil is obtained which is chromatographed on silica, eluant: n-hexane / ethyl acetate (9:1). 1.55 g of the product sought are thus obtained. /a/n : +52° - 2.5° (c = 0.5%, chloroform). g"7 Example Sff: (RS) cyano 2-(6-phenoxyx>yridyl) methyl (IR cis. Az) 2,2-dimethyl 5-(3-oxo 3-allyloxy 1-pronenyl) cyclopropane carboxylate. S3 Work being carried out as in Example ■&*?, starting with 2.1 g of (RS) cyano 2-(6-phenoxypyridyl) methyl (IR cis, Az) 2,2-dimethyl 3-(3-oxo 3~bydroxy 1-propenyl) cyclopropane carboxylate, prepared as indicated in Stage D of Example 84-, 3 and 0.8 cnr of allyl alcohol, an oil is obtained which is chromatographed on silica, eluant: n-hexane / ethyl acetate (85:15). 1«55 g of the product sought are thus obtained. /a/D : +53° - 3° (c = 0.3%, chloroform). Example 3-Fhenoxyphenyl methyl (IR cis,Az) 2,2-dimethyl 3-[3-0x0 3-(l,l-dimethyl propoxy) propenyl] cyclopropane carboxylate. Stage A: j-Phenoxyphenyl methjl__(l^R_cis_^ Az^_ 2,£-dimethjl ^-_[32.°2E°_3z.(1.>^Zl_-PZ.O£°S7l. £r£P2PZl.i cyclo£ro£ane_ £arb 6x^1 at e,. 3 g of product obtained according to Stage B of Example J&5", 3 cm-5 of methylene chloride, 1 cnr of tert-amyl alcohol and 0.1 g of dimethylaminopyridine are mixed. Under agitation and at +5°C, 1.75 g of dicyclohexylcarbodiimide in 1 cnr of methylene chloride are added and the whole is 197175 allowed to return to ambient temperature and agitated for 4- hours 30 minutes. It is filtered, the filtrate is brought to dryness under reduced pressure and the residue is chromatographed on silica (eluant: hexane / ethyl acetate, 5 8:2). 1.05 g of expected product are obtained. Stage B: ^-Ihjjnoxjphenyl meth£l_(i is_j_ Az_}_ £»2-dime>th2l-_ ^-[3-0x0 ^-(1,1-dimejthjrgropoxy) propenyl]_c^clopropane^ c_a£b£X2la te . Hydrogenation of 1.05 g of the product obtained in *5 10 the previous stage in 20 cnr of ethyl acetate is carried t out in the presence of 0.2 g of 10% palladium hydroxide on barium sulphate and 0.2 cm^ of quinoline. The product is filtered, the filtrate is washed with 0.1 F hydrochloric acid then with water, it is dried, it is concentrated to 15 dryness under reduced pressure, the residue is chromatographed on silica (eluant: hexane / ethyl acetate, 95:5) and 0.756 S of the expected product is obtained. /a/D : +56.5° ~ 2.5° (c » 1%, chloroform). •• (o°i 107i?e o E? < n O > TO oo 4*. 10 15 20 i\j m z H O n n Preparation 1: (IE cis, AZ) 2,2-dimethyl 3-[3(methoxy-5-oxo--1-propenyl] cyclopropane carboxylic acid. Stage 1_: Tejrtbutyl _£lR cis.)_2A2-djlm^t hyl £[ me 1: h^x^-^oxo l-jDrop^n^U cyclopro£ane_cart>oxylat;ej_ 55 S of tertbutyl (IR, cis) 2,2-dimethyl 3~(2,2- -dibromovinyl) cyclopropane carboxylate are introduced * into 550 cnr of tetrahydrofuran. The whole is cooled to -70°C and, over 40 minutes, 132 cm^ of a solution of butyl lithium in cyclohexane (at 20%) is added and the whole is o 3 agitated for 30 minutes at -65 C. 12.5 car of methyl chloroformate are then added. After 2 hours' reaction at -70°C, the temperature is allowed to rise again to -20°C and the mixture obtained is poured into an aqueous solution of monosodium phosphate and the whole is extracted with ether. It is washed, dried and brought to dryness under reduced pressure. 38.3 g of a product are thus obtained, which is chromatographed on silica, elutant: cyclohexane / ethyl acetate (8:2). 17.2 g of the product sought are thus obtained. .Stage. 13: Tertbutyl _£lR cis., AZQ. £,2-dimeth^l__3-[^-methoxx .2.-OXO. 1-propenyl] eyelopro^ane_carboxylate^ Hydrogenation of 12 -g of the product prepared in Stage A in 240 cm^ of ethyl acetate is carried out in the presence of 2.4 g of 10% palladium hydroxide on barium sulphate and 2.4 cm^ of quinoline. The whole is filtered and dried. llg of the product sought are thus obtained. Stage £: Xl£ _£i_£ v4Z)_2_12_2d_imethyl ^~^3-™£thoxy-3j-oxo_ _l-jDrop_en£l]_ _cyclop_ropane_c_arboxylic _acid._ no 1971?5 -j/r- A solution containing 13*5 g of the product prepared in Stage B, 100 cm^ of toluene and 400 mg of hydrated paratoluene sulphonic acid is taken to reflux for 3 hours. It is brought to dryness under reduced pressure and 11.2 g of a product are obtained which ischromatographed on silica, eluant: cyclohexane / ethyl acetate / acetic acid (60:39:1)- It is brought to dryness under reduced pressure and 9.6 g of the product sought are obtained, melting at 110°C. Ca] 20 .or- Po + D = +75.5 - 2U (c = 1%, CHCl^) NMR : CDCl^ in p.p.m. 1.3 : protons of the methyls at 2 of the cyclopropane, 1.86-2 : proton at 1 of the cyclopropane, 3.1 - 3.28 - 3.4-3 : proton at 3 of the cyclopropane, 5«8 - 5-99 : ethylenic proton at a of the C02CH^ group, 6.4-2 - 6.58 ): ) ethylenic proton at B of the CO^CH, group, 6.61 - 6.77 ): 5 8.63 : proton of the CO2H group, 3-71 : protons of the methoxy. Preparation 2: (IR cis, AZ) 2,2-dimethyl 3-/3-ethoxy 3-oxo 1-propenyl] cyclopropane carboxylic acid. Stage. 1: Tej?tbutyl _£lR cis.)_2A2^dimethyl ^.(^.-hydr£X2 j5-oxo l~j^rop2njl)_ eye lop_rop am.e_c arboxyl a te^ 26 g of tertbutyl (IR cis) 2,2-dimethyl 3~(2,2- dibromovinyl) cyclopropane carboxylate are introduced into z -z 175 cnr of anhydrous tetrahydrofuran. 60 cnr 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 # ■ , 197175 ni " ~ 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 5 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 are then obtained, melting at 144°C. 10 NMR : CDCl^ in p.p.m. 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 -C-OH group. 0 15 Stage. B: Tertbutyl £lR cis.)_2j_2^_di_me.thyl ,^(^-£thoxy_J5^oxo_l- -propynyl) cvclogropane ca£box2lat£. 4 g of the product prepared in Stage A, 3.4 g of dicyclohexylcarbodiimide and 6 mg of 4-dimethy1amino pyridine are introduced into 30 cnr of methylene chloride. ■z. 20 1.5 cm of ethanol are then added aid. the whole is agitated for 16 hours at 20°C. It is filtered and the filtrate is concentrated under reduced pressure. 5-5 E of a product are thus obtained which is purified by chromatography on silica, eluant: cyclohexane / ethyl 25 acetate (9:1). 4.25 S of the product sought are thus obtained. N.Z. PATENT OFFICE 14 MAR S984 10 15 20 25 n*-- j?i - HM5 : CDClj in p.p.m. 1.18 - 1.21 and 1.36 - 1.47 1.73 and 1.82 1971?5 protons at 2 of the cyclopropane, protons at 1 and 3 of the cyclopropane, protons of the tertbutyl, protons of the ethyl. 1.47 1.27 - 1.38 - 1.5 4.0 - 4.13 ~ 4.25 - 4.36 Stage C: Tertbutyl £lE .cis,_42)_2^2-dimethyl ^-(Ji^ethox^ 3t2.x2. _l~£r£P£.nZl). cyclopropane carboxylate. Hydrogenation of 4.3 g of the product prepared in the previous stage in 100 cm^ of ethyl acetate is carried out in the presence of 800 mg of palladium hydroxide on barium sulphate and 0.8 cm^ of quinoline. The whole is filtered and the filtrate is brought to a pH below 7, with 2N hydrochloric acid, and washed with water. It is dried and brought to dryness under reduced pressure. 4.6 g of a product are obtained which is chromatographed on silica, eluant: cyclohexane / ethyl acetate (95:5). 2.5gof the product sought are thus obtained. NKR : CDCl^ in p.p.m. 1.25 ~ 1-28 1.78 - 1.93 2.98 - 3.1 - 3-2 6.4 — 6.6 - 6.8 protons of the methyls at 2 of the cyclopropane, proton at-1 of the cyclopropane, proton at 3 of the cyclopropane, proton of the ethylenic carbon at a of the cyclopropane, patent office _ » y 5-7 - 5-9 :proton of the ethylenic carbon "bearing the ethoxy carbonyl group, 4.0 - 4.13 - 4.25 - 4.36 :proton of the methylene of the ethoxy. 5 .Stage D: (JLR cis. >_AZ)_2^2^ddjn£thyl ^"X5z.etbox2 ^-oxo l-^ropenjlJ. cy_c l£p_ro£ane_c_arboxyl ic £ciAi. 2.3 g of the product prepared in Stage C and 20 mg of hydrated paratoluenesulphonic acid are introduced into 20 cm^ of toluene. The whole is taken to reflux for 40 10 minutes and brought to dryness under reduced pressure and 2.1 g of a residue are thus obtained which is chromatographed on silica, eluant: cyclohexane / ethyl acetate / acetic acid (60:39:1)- 1-7 S of the product are isolated which is recrystallisedfrom cyclohexane. 1.5 g of the product 15 sought are thus obtained, melting at 96°C. NMR : CDCl^ in p.p.m. 1.3 and 1-32 .: protons of the methyls at 2 of the cyclopropane, 1.86 - 2.02 : proton of the carbon at 1 of the cyclopropane, 3.15 - 3-28 ) 20 3.3 - 3-45 6.38 - 6.53 ): proton of the branched ethylenic carbon on 6.55 - 6.73 ]: the' cyclopropane, 5-78 - 5-96 : proton of the ethylenic carbon bearing the ethoxy carbonyl group, 1.18- 1.3 - 1-41 : protons of the methyl of the ethoxy carbonyl group, 4.0 - 4.13 protons of the methylene of the ethoxy 4.25 - 4.36 ): carbonyl group. proton of the carbon at 3 of the cyclopropane, JUT * -yf- Preparation 3* (IR cis, AZ) 2,2-dimethyl 3[3-propoxy 3-oxo 1-propenyl] cyclopropane carboxylic acid. Stage A: Tertbutyl _£lR cis.)_2 A2-dimethyl j^-£ropox£ ^r£xo l-£r op^£l_cjc Jjdjd r opane j^arbox^late. 5 22.8 g of tertbutyl (lR-cis) 2,2-dimethyl 3-(2,2--dibromovinyl) cyclopropane carboxylate, 250 cm^ of tetra-hydrofuran then, at -60°C, 55 cm^ of a 20% solution of butyl lithium in cyclohexane are introduced. The whole is maintained at -65°C for 1 hour and, at -65°C, over 15 ■z 10 minutes, 8 cur of n-propyl chloroformate are introduced. The agitation is maintained for 1 hour at -65°C and the whole is allowed to rise again to ambient temperature over 1 hour and is agitated again for 1 hour at ambient temperature. It is poured on to a saturated aqueous solution of monosodium 15 phosphate and the whole is agitated, extracted with ether and washed with water. It is dried and brought to dryness under reduced pressure. 19-5 g of an oil are thus obtained which is purified by chromatography on silica, eluant: cyclohexane / ethyl acetate (9:1)- 11-'5 S of the expected 20 product are thus obtained. NMR Spectrum CDCl^ in p.p.m. 1.17 and 1.37 • protons of the methyls at 2 of the 25 1.44 4.0 - 4.12 - 4.23 1.72 cyclopropane, protons at 1 and 3 of the cyclopropane, protons of the tertbutyl, proton of the methylene at 1 of the propoxy carbonyl, To - R<- 1 ^ ~L %J $ Ji * O 10 15 25 0.83 - 0.95 - 1.06 : protons of the methyl of the propoxy carbonyl. Stage B: Tertbutyl £lR £is,_AZ)—2J_2-dimeithy_l ^-_[3zPZ°£.°2Dr__ 2~£x£. ]r2r2J>£PZ^2. £^£^oprp^ane_carbo xylate^ 7 g of tertbutyl (lR,cis) 2,2-dimethyl 3~(n-propoxy 3-oxo-l-propynyl) cyclopropane carboxylate in 140 cm^ of ethyl acetate are hydrogenated in the presence of 1.4 g of 10% palladium hydroxide on barium sulphate and 1.4 cm^ of quinoline. The filtrate is washed, using a 2N solution of hydrochloric acid, then it is washed with water, dried and brought to dryness under reduced pressure. 7«2 g of a product are thus obtained which is chromatographed on silica, eluant: cyclohexane / ethyl acetate (95;5)» 6.1 g of the product sought are thus obtained. NMR Spectrum CDC1, in p.p.m. 1.25 and 1.29 1.5 to 2.03 20 3.03 to 3-35 6.5 - 6.66 6.69 - 6.85 5-82 - 6.0 ) ) ) 4.02 - 4.12 - 4.23 m.z. patent office proton of the methyls at 2 of the cyclopropane, proton of the carbon at 1 of the cyclopropane, proton of the carbon at 3 of the cyclopropane, proton of the ethylenic carbon bonded to the cyclopropane, proton of the ethylenic carbon bearing the propoxy carbonyl group, proton of the methylene at 1 of the propoxy carbonyl group, 14MA& 1984 -J#- \ fn'ri ;y <r i- ^ f 1 t y 0.86 - 0.98 - 1.1 : proton of the methyl of the propoxy carbonyl group. Stage C^: £lR ci^,_AZ )_2^2^d ijn^t hyJL ^-_[3zJPX°£°2E7_3^.oxo_ l-^ropen^lj. £yclopj?0£ane__C£rboxylic. jicid^ A mixture of 5*8 g of the product prepared in Stage B, 7. 200 mg of hydrated paratoluene sulphonic acid and 60 cnr of toluene is taken to reflux for 1 hour. It is brought to dryness under reduced pressure and 5 S of a product are obtained which is chromatographed on silica, eluant : cyclohexane / ethyl acetate / acetic acid (70:29:1). 4.2 g of the product sought are obtained. NMR Spectrum CDCl^ in p.p.m. 1.27 and 1.29 : H of the methyls at 2 of the cyclopropane, 1.86 - 2 : H at 1 of the cyclopropane, 3.13 to 3.45 : H at 3 of the cyclopropane, 5.8-6 : H of the ethylenic carbon bearing the CO2CH2CH2CH2 group, 6.4 - 6.56 - 6.59 : H of the ethylenic carbon bonded to the cyclopropane, 3.98 - 4.08 - 4.18 : H of the methylene at 1 of the propoxy carbonyl group, 0^83 - 0.95 ~ 1.06 : H of the .methyls of the propoxy carbonyl group. Preparation 4: (IR cis, AZ) 2,2-dimethyl 3-C3-(l-methyl-ethoxy) 3-oxo-1-propenyl] cyclopropane carboxylic acid. Stage A: Ter;tbutyl_ _£_1R cis_,_AZ)_2^2^dimethyjl 1-oxo JL-j>ropen£l]_ cjclopro£ane_carboxylatej^ n.z. patent pff:-,s 14 MAR 1984 lUCBWBD nl 197175 - 7?- 2 g of tertbutyl (IS cis) 2,2-dimethyl 3C3_bydroxy 3-oxo 1-propynyl] 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 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. Stage B: Tertbutyl _£1R £i£,_A2)_2^2^dimethyl 2"i3~(lrJ£eth2l-e^thoxy2~2r£x2. 2Tllr£P£n2ll2. cy£lop£ojDane_carboxylat_e_;_ 2.7 g of tertbutyl (IB cis) 2,2-dimethyl 3-E(Z) 3-hydroxy 3-oxo 1-propenyl] cyclopropane carboxylate are mixed into 10 cm^ of ethyl acetate, then 2 g of 0-isopropyl N, N'-diisopropyl isourea are added and the whole is agitated for 1 hour at ambient temperature. It is taken to reflux for 1 hour 30 minutes and allowed to return to 20°0, the insoluble matter is filtered and the filtrate is brought to dryness under reduced pressure. 3-5 g of an oil are obtained which is chromatographed on silica, eluant: benzene / cyclohexane (7:3) • 1 g of the product sought is thus obtained and used as it is in the following stage. Stage C: £lR £is,_AZ)_2A2-dimethyl 1-mejfchjl-ethoxj) j$-£XO_ JL-£ropen£l]_ eye lop ropane_ carboxylic jicicL A mixture containing 1.4 g of tertbutyl (IB cis, AZ) 2,2-dimethyl 3-C3-(l-methylethoxy) 3-oxo 1-propenyl] cyclopropane carboxylate, 100 mg of paratoluene sulphonic acid fi -yr- 197175 t. 0 and 14 cnr of toluene is taken to 120 C under agitation for 2 hours 30 minutes. It is "brought to dryness under reduced pressure. A residue is obtained which is recrystallised from isopropyl ether. It is chilled, separated and dried and 900 mg of the product sought are thus obtained, melting at 98°C. Preparation 5: (IR cis, AZ) 2,2-dimethyl 3-(5-cyclobutyloxy 3-oxo 1-propenyl) cyclopropane carboxylic acid. .Stage, A: JTejrtbutyl _£lR cis_,_AZ )_2JL2^d im^t hy 1, j5-^2c7£l£^.iit2rl-0x2 .2r£x£ l~propenylJ)_ eye lopropane_c arboxylate. 4 g of tertbutyl (IE cis, AZ) 2,2-dimethyl 3-C3-bydroxy 3-oxo 1-propenyl] cyclopropane carboxylate are dissolved in 20 mg of methylene chloride then 1.7 mg of cyclobutanol are added. The temperature is lowered to 0/+5°C, 3«45 g of dicyclohexylcarbodiimide and 28 mg of dimethylaminopyridine in 20 mg of methylene chloride are added and the agitation is maintained for 2 hours at about 5°C and- 2 hours at ambient temperature. The dicyclohexylurea formed is eliminated and the filtrate is concentrated to dryness and chromatographed on silica, eluting with a n-hexane / isopropyl ether mixture (9:1)- 2.3 g of expected product are obtained. Stag.e B: £lR cis.,_AZ )_2j.2^di.m£thyJL 3-( 3~cyclobutyloxy 3-oxo l-jDropen^ri^. cy^loprojgane_c^rbo2cyli£ acid^ ■x 2.3 g of the product obtained previously, 25 cnr of toluene and 250 mg of paratoluene sulphonic acid are heated to reflux for 15 minutes, cooled and agitated for 2 I ^ -fin* tr (-i -t 22 -ye- hours at 0/4-5°C. The insoluble matter is filtered and the filtrate is concentrated to dryness for 1.8 g of expected product. IR Spectrum 5 - OH : acid 3500 cm-"*" - 0=0: acid 1733 cm~^. + ester oonj 1702 cm" ^ gem. di Me : 1390 crn-^" 1380 cm"1 10 Preparation 6: (IR cis, AZ) 2,2-dimethyl 3-C5-(RS) 1-methvl--propyloxy) 3-oxo 1-propenyl] cyclopropane carboxylic acid. Stage A: Tertbutyl _£1R £is_)_2j2^dim£thyl 2~-L3JL®S ) hyl 2ro.PZ3._oxy ^-oxo. lr^rop^n^lj. cyclop^o^ane^^rbo^cyla^e^ 4 g of tertbutyl (IR, cis) 2,2-dimethyl 3_(3_bydroxy 15 3-oxo 1-propynyl) cyclopropane carboxylate, 40 cm^ of methylene chloride and 6 mg of 4--dimethylamino pyridine are mixed then 3-4- g of dicyclohexylcarbodiimide are added. After 30 minutes' agitation under inert atmosphere 2 cm3 of methylene chloride and 2 cm^ of 1-methyl propanol are 20 added over 5 minutes and the agitation is maintained for 3 hours at ambient temperature. The dicyclohexylurea formed is filtered, the filtrate is concentrated to dryness under reduced pressure and the residue is chromatographed. on silica, eluting with a n-hexane / isopropyl ether mixture (8:2). h :| ^ 2 | 3*5 B of the expected product are obtained. £ ' \ I ,1 i l ) | Stage B: Tertbutyl £1R £is.,__^)_2j.2^di.m£thyl 2^~X^)__lzm®thyl propyloxy 2""5LX£ 1-propenyl] cyclopro£ane__c arboxylate^ 'ml 10 15 20 is. s /t? <gt> srf"- 107175 3 g of the product obtained previously are hydrogenated as indicated in preparation 4. The product is chromatographed on silica eluting with a n-hexane / isopropyl ether mixture (9^1) and 2.5 g of expected product are obtained. Stage. C: _£lE cis ,_AZ)_2^2-dimethyl 2~_L hr l^methYl _gropy- l°xy) 3-oxo_ l-propenyl/_ cyclopropane _ca_rbo_x2,l_ic_ac_id;. 3 g of product obtained above are agitated with 250 mg of paratoluene sulphonic acid in 25 cm^ of toluene. The whole is heated to reflux until the release of gas has ceased. It is concentrated to dryness under reduced pressure and the residue is chromatographed on silica eluting with a mixture of cyclohexane, ethyl acetate and acetic acid (70:30:1). 1.85 g of expected product are l obtained. IE Spectrum (CHCl^) - OH : acid - C=0 : acid ester C=C conj gem. di Me 35IO cm 1735 cm" 1170 cm" 1637 cm 1381 cm" Preparation 7: (IE cis, AZ) 2,2-dimethyl 3[3-oxo 3-(cyclo-propylmethoxy)] propenyl cyclopropane-l-carboxylic acid. Stage A: Tertbutyl JLlE,_cis_2. AZ.2 Z.cZPlP2.r2PZl™et.h£X2;]_P£°£enyl cycl£propane2.l2.c>arboxylate>;_ 20 g of tertbutyl (IE cis, AZ) 2,2-dimethyl 3(3~bydroxy 3-oxo 1-propenyl) cyclopropane 1-carboxylate and 6.2 g of 3 cyclopropylcarbinol are introduced into 150 cnr of methylene « 1971?, - £6 - chloride, 2 g of dimethyl aminopyridine and 17-5 S of x dicyclohexylcarbodiimide in solution in 60 cnr of methylene chloride are added, the whole is agitated for 2 hours at 20°C, the insoluble matter formed is removed from the preparation, the remainder is concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica, eluting with a mixture of hexane and isopropyl ether (9:1) and 12.32 g of tertbutyl (IR cis, AZ) 2,2-dimethyl 3C3~oxo 3-cyclopropylmethoxy] propenyl cyclopropane-l-carboxylate are obtained. Stage B: £3.11 _cis,_AZ)_2JL2^dimethyl ^l^~oy:o_ metho__P£0£enyl cy£lop£0£ane-l^_ca.rboxylic_ apid^ 12.32 g of tertbutyl (IR cis, AZ) 2,2-dimethyl 3-[3-0x0 3-oyclopropylmethoxy] propenyl cyclopropane-1--carboxylate and 0.6 g of paratoluenesulphonic acid are introduced into 120 cm^ of toluene, the whole is taken to reflux, the refluxing is maintained for 4-5 minutes, the whole is cooled and concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica eluting with a mixture of hexane and ethyl acetate (7:3) containing 1% of acetic acid and 8.94- g of (IR cis, AZ) 2,2-dimethyl 3[3-oxo 3~cyclopropyl-methoxy] propenyl cyclopropane-l-carboxylic acid are obtained, M.Pt. = 106°C. NMR Spectrum (CDCl^) p.p.m. 1.29 - 1.31 protons of the geminal methy|.-s 1.13 proton of the - CH"C - 03T- 197175 2 3> *3 oo 10 15 20 5 ¥ m O ■71 2} o m 1.85 "2 2 proton at 1 of the cyclopropane 3.9-4- proton of the 0 - CH2 < 5-82 - 6.01 and from 6.4-2 to 6.77 cis ethylenic protons. Preparation 8: (IR cis, AZ) 2,2-dimethyl 3-(3-oxo 5-tert-butoxy propenyl) cyclopropane carboxylic acid. Stage A: Methjl^Cl.R^ cis.)_2_l2^dim ethy 3. 2~J!i72Lr.2?C£ propenyl] cy^lopi^ojaane-l^carboxylate^ 36-5 g of methyl (IR, cis) 2,2-dimethyl 3-(2,2-dibromo-ethenyl) cyclopropane-l-carboxylate are introduced into 360 cm^ of tetrahydrofuran, 100 cm^ of 20% suspension of butyl lithium in cyclohexane are added at -70°C, the whole is agitated for 10 minutes, carbon dioxide is bubbled in for 30 minutes, the temperature is allowed to rise again to -20°C, the reaction mixture is poured on to a mixture of water, ice and sodium bicarbonate, the whole is extracted with ethyl ether and washed with water, the aqueous phases are acidified and extracted with ether, the combined organic phases are washed with water and they are concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica eluting with a mixture of cyclohexane and ethyl acetate (6:4-) containing 1% of acetic acid and 6.8 g of methyl (IRj cis) 2,2-dimethyl 3C3~oxo 3-hydroxy propynyl] cyclopropane-l-carboxylate are obtained. Stage B: Meth2.1_(lRj_ cis.)_2_t2^_dim^thyl ^1%-oxo^-^-teTt^ bu to xy_j? r;opyny l] _c^c Iojd ropan£~ l-£&rb o_x£la t£ . 6.8 g of methyl (IR cis) 2,2-dimethyl 3(3~oxo 3-bydroxy •z propynyl) cyclopropane-l-carboxylate are introduced into 10 cnr 197175 of ethyl acetate, 13-5 g of 0-tert-outyl N, N* diisopropyl the insoluble matter formed is removed by filtration, the filtrate is concentrated to dryness, the residue is chromatographed on silica eluting with a mixture of cyclohexane and ethyl acetate (85:15) and 7 g of methyl (IR, cis) 2,2-dimethyl 3[3~oxo 3-tert-butoxy propynyl] cyclopropane-l-carboxylate are obtained. Stage C_: Methjl_(l_Ra_ ci£,_AZ )_2^2-djmet hy 1, ^.l^-oxo, Srtert^ bu1:oxy^l;jDrp£enyl]_c^clp^ropan^l^^arboxjl^te^. At 20°C, in the presence of 10% palladium hydroxide on barium sulphate and 1.4 cm^ of quinoline, 7 g of methyl (IR, cis) 2,2-dimethyl 3[3~oxo 3-tert-butoxy propynyl] ■z. cyclopropane-l-carboxylate in 14-9 cnr of ethyl acetate are hydrogenated. The product is filtered, the filtrate is washed with N hydrochloric acid, then with water, it is dried and it is concentrated to dryness by distillation under reduced pressure and 5-8 g methyl (IR cis, AZ) 2,2-dimethyl 3t3-oxo 3-tert-butoxy 1-propenyl] cyclopropane-l -carboxylate are obtained. Stage D: £lR cijs,_AZ)_2^2-dimethyl 2,l2r2.x2. 2~jieZt^but£X2-l-_ ^pro^enyl]_cyclopropane-1-carboxylic acid. 2.5 g of methyl (IR, cisAZ) 2,2-dimethyl 3[3-0x0 3-tert-butoxy-1-propenyl) cyclopropane-l-carboxylate are introduced into a mixture of 25 cm^ of methanol and 9-8 cm^ of N aqueous solution of sodium hydroxide, the whole is agitated for 3 hours at 50°C and cooled to -75°C, the urea are added at -*-15°C, the whole is agitated for 2 hours 197175 «* -J*" reaction mixture is poured into water and extracted with ethyl ether, the aqueous phases is acidified to pH 1 with hydrochloric acid and extracted with ether, the organic extracts are concentrated to dryness hy distillation under reduced pressure, the residue is chromatographed on silica eluting with a mixture of cyclohexane and ethyl acetate, 7 '5, containing 1% of acetic acid and 1-576 g of (IE, cis AZ) 2,2-dimethyl 3C3-oxo 3-tert-butoxy propenyl] cyclopropane-1--carboxylic acid are obtained. IR Spectrum (CHCl^) Absorption at 3500 cnf^" attributed to the acid OH (monomer + dimer) Absorptions at 1730 crn"^" and 1695 cm~^ attributed to the acid C=0 and ester Absorption at 1628 cm~*^ attributed to the conjugated C=C Absorptions at 1390 cnf*^" and 1377 cm ^ attributed to the geminal methyls Absorption at 1368 cm~"^ attributed to the tertbutyl. Preparation 9: (IE cis, AZ) 2,2-dimethyl 3-(3-isobutyloxy 5~oxo 1-propenyl) cyclopropane-1-carboxylic acid. Stage A: Tertbutyl £1R cas_,_AZ)_2^2^dimethyl 2-£3-ijLobu£oxy__ 2-oX£-l7£ropeii2l)_ cyclop.ro]3 an e^l-car boxy 1 ate Into 10 cm^ of methylene chloride and 1 g of isobutanol are introduced 4 g of tertbutyl (IE cis, AZ) 2,2-dimethyl 3-(3-hydroxy 3-oxo 1-propenyl) cyclopropane-l-carboxylate, prepared according to preparation 4 Stage A, then, at 0°C, 2.8 g of dicyclohexylcarbodiimide. and_30- mg of dimethylamino- 197175 - pyridine in solution in 10 cm^ of methylene chloride are added, the whole is agitated for 17 hours at 60°C, the insoluble matter is eliminated by filtration, the filtrate is concentrated to dryness for distillation under reduced pressure, the residue is chromatographed on silica eluting with a mixture of cyclohexane and isopropyl ether (9:1) and 2.1 g of tertbutyl (IE cis, AZ) 2,2-dimethyl 3~(3~ -isobutoxy 3~oxo 1-propenyli) cyclopropane-l-carboxylate are obtained. Stage B: _£lE £i_s,_AZ)_2_L2j^dim^thyl 2(2~is£kutox2[ ^-oxo l_-£ropenjl2. eye lopropane-1-c j^boxylic aci^d_-_ Into 20 cm^ of toluene are introduced 2.1 g of tertbutyl (IE cis, AZ) 2,2-dimethyl 3-(3~isobutoxy 3~oxo 1-propenyl) cyclopropane-l-carboxylate and 0.1 g of paratoluene sulphonic acid, the whole is taken to reflux and maintained there for 20 minutes, concentrated to dryness by distillation under reduced pressure and chromatographed on silica eluting with a mixture of hexane and ethyl acetate (7^3) containing 1% of acetic acid and 1.53 g of (IE cis, AZ) 2,2-dimethyl 3~(3-isobutoxy 3-oxo-1-propenyl) cyclopropane- 1-carboxylic acid are obtained. IB Spectrum (chloroform) ^ Absorption at 3300 cm \ attributed to the acid OH Absorption at 1730 cm~~^, 1706 cm""\ 1694 cm ^ attributed to the acid C=0 and conjugated ester Absorption at 1630 cnf"^ attributed to C=C (.az) Absorption at 1390 cm-"'", 1380 cm"^ attributed to the geminal methyls. <£io -J&- 197175 Preparation 10: (IB, cis AZ) 2,2-dimethyl 5-(3-n butoxy 3-oxo 1-propenyl) cyclopropane carboxylic acid. Stage, A: Tertbutyl £lE,_cis2, 2,2-d i m e t; hxL_3 -(2,-n butoxy_ 1-oxo l.""£r£PLnZl^L cyclopropane carboxjla3ie^- 4 g of tertbutyl (IE, cis) 2,2-dimethyl 3-(3~kydroxy 3-oxo 1-propynyl) cyclopropane carboxylate, 40 cm^ of methylene chloride and 6 mg of 4-diethylaminopyridine are mixed then 3-4 g of dicyclohexylcarbodiimide are added. After 30 minutes' agitation "under inert atmosphere there are added, over 5 minutes, 4 cm^ of a mixture (1:1) of n-butanol and methylene chloride and the agitation is maintained for 3 hours at ambient temperature. The dicyclohexylurea formed is filtered, the filtrate is concentrated to dryness tuader reduced pressure and the residue is chromatographed on silica, eluting with a cyclohexane / ethyl acetate mixture (9:1)- 4.7 g of the expected product are obtained. Stage, B: Tertbutyl £lB,_ciSj_ AZ). £,2-dimeth£l_3-Q-n butoxy_ _2.-o,x£-l_-Ilrjopen£l)_ cyclop;ro]Dane_carboxy.late.:_ 800 mg of palladium hydroxide on barium sulphate in 20 crn^ of ethyl acetate are agitated under hydrogen for 15 minutes, then 4.7 g-of product obtained above in 50 cm^ of ethyl acetate and 0.8 cm^ of quinoline are added and the whole is left under hydrogen for 30 minutes. It is filtered, the filtrate is washed with N hydrochloric acid then with water, dried and concentrated to dryness . under reduced pressure and the residue is chromatographed *1 -JB6-- 197175 on silica eluting with a cyclohexane / ethyl acetate mixture (95:5)- 3-4 g of expected product are obtained. Stage _C: £lR cis.,_AZ)_2^2^dim^thy 1_ hut_oxy_3-oxo^_l- ;jD£0£enyl]_c£clpjjropane ^arb^x^li c_acid. 3.3 g of product obtained above are agitated with 350 mg of paratoluene sulphonic acid in 40 cm^ of toluene. The whole is heated to reflux until the release of gaseous isobutylene has ceased, that is about 40 minutes. The remainder is concentrated to dryness under reduced pressure and the residue is chromatographed on silica eluting with a mixture of cyclohexane, ethyl acetate and acetic acid (75:25:1). 2 g of expected product are obtained. NMR CDC1, p.p.m. 1.26 and 1.3 : protons of the methyls at 2 of the cyclopropane , 1.85-1.99 : proton at 1 of the cyclopropane, 3.13 to 3.47 : proton at 3 of the cyclopropane, 6.4 - 6.57 and 6.59 - 6.75 • proton at 1 of the allyl chain, 5-8 - 5-99 : proton at 2 of the allyl chain. Preparation 11: (IR cis, AZ) 2,2-dimethyl 3-(3-cyclopentoxy 3-oxo 1-propenyl, cyclopropane-l-carboxylic acid. Stage A: Tertbutyl £lR c_i_s,_AZ)_2J_2^di1ine_thyl 2-X.3z.cZci°£e£.toxy 3>- oxo-l-propen%l) eye lopropane-1-carboxylate. 7> Into 15 cnr of methylene chloride are introduced 4 g of tertbutyl (IR cis, AZ) 2,2-dimethyl 3-(3~kydroxy 3-oxo--1-propenyl) cyclopropane-l-carboxylate and 1.43 g of cyclo-pentanol, at 0°C, 3.43g of cyclohexylcarbodiimide and 40 mg 107-1.7-: _ 0 * -i i u of dimethylaminopyridine in solution in 10 cm^ of methylene chloride are added, the suspension is agitated at 20°C for 17 hours, the insoluble matter is eliminated by filtration, the filtrate is concentrated to dryness by distillation under 5 reduced pressure, the residue is chromatographed on silica eluting with a mixture of cyclohexane and - isopropyl ether (9:1) and I.38 g of tertbutyl (IE cis, AZ) 2,2-dimethyl 3~(3" -cyclopentoxy 3-0x0 1-propenyl) cyclopropane-l-carboxylate are obtained. 10 M.Pt. = 57°C. Stage, B: _£lR ci_s,_AZ)_2JL2^dim_e_thyl 2-X5z.cZci°JEeSt£32-2-£xo. _l-_2ropenzlJ. cy^lop^o^ane-l-carbojcyli^ aci^d^ i 7. Into 25 cur of toluene are introduced 2.5^ g of tertbutyl (IE cis, AZ) 2,2-dimethyl 3-(3-cyclopentoxy 3-oxo 15 1-propenyl) cyclopropane-l-carboxylate and 0.1 g of paratoluene sulphonic acid, the whole is taken to reflux, the refluxing is maintained for 20 minutes, the whole is concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica, eluting 20 with a mixture of hexane and ethyl acetate (7:3) containing 1% of acetic acid and 1.82 g of (IB cis, AZ) 2,2-dimethyl 3-(3-cyclopentoxy 3-0x0 l-pxopenyl) cyclopropane-l-carboxylic acid are obtained. IR Spectrum (chloroform) 25 Absorption at 3510 cm~^ attributed to acid OH Absorptions at 1735 cn* \ 1702 cm attributed to acid C=0 N.Z. PATZil'T OFFICE 14 MAR 1984 RECEIVED and the conjugated ester. «1 1971? - >86"- Absorption at 1632 cm~^ attributed to conjugated. C=C Absorption: at 1380 cnT^" attributed to geminal methyls. Preparation 12:(1B trans, AZ) 2.2-dimethyl 3- C 3- (1--methylethoxy) 5-oxo 1-propenyl] cyclopropane carboxylic acid, Stage A: Tertbutyl _(1R trsns_)_2j_22.dime_thyl ^-^^hyd roxy__3^.ox° l-^rop^nzlX cyclopro^ane^jirbpxylate^ Work is carried out as in Stage A of Preparation 2, starting with 40 g of tertbutyl (IE trans) 2,2-dimethyl 3-(2,2-dibromovinyl) cyclopropane carboxylate. After chromatography on silica of the crude product (eluant: cyclohexane / ethyl acetate / acetic acid, 6:4:0.2) 19.2 g of the expected product are obtained. Stage B: Tertbutyl _£1R trans)_2j_2-dimethyJL l-^_3£l^me_thyl-ethoxyj), 2~oxo .l-jsrop^nyl]. cyclopropane_ . c arboxyl ate^. 3-6 g of product obtained according to the previous stage are mixed into 20 cm^ of ethyl acetate, 3 g of 0-isopropyl N, N' diisopropyl isourea are added and the whole is agitated for 16 hours at reflux. After a return to ambient temperature, it is filtered, the filtrate is concentrated to dryness under reduced pressure and 2.7 g of expected product are obtained. Stage C: Tertbutyl _£_1R trans_,_AZ)_2_1_2^.di_methyl_ 3- C3(l-methyl-.ethoxy). j£~oxo ^-propenyl] c^l_opr_ooane_carboxyA 2.7 g of the product obtained in the-previous stage in 50 cm^ of ethyl acetate are hydrogenated in the presence of 0.55 g of 10% palladium hydroxide on barium sulphate and 0.55 of quinoline. The product is filtered and the filtrate is washed with N hydrochloric acid then with water > Ho - W- 1971?S until neutral, dried, and concentrated, to dryness under reduced pressure. 2.18 g of the expected product are . < obtained. Stage D: (l_R__trans_j_ AZ)_ ^,£-dimettizl^C3^(lrmethxl£tho2cy2. 5 l~£xo_ l~£rope_nzlj. eye l0pr_02ane_c a^boxylic. a-cid^ 2.18 g of the product obtained in the previous stage,. 20 cnr of toluene and 0.2 g of paratoluene sulphonic acid are taken to reflux. After a return to sanhient temperature, the organic phase is washed with water, it is dried and concentrated 10 to dryness under reduced pressure. 1.6 g of expected product are obtained. Preparation 13? 5-phenoxy q-hydroxy benzene ethane thioamide. Into a solution of 20 g of a-cyano3~phenoxybenzyl 15 alcohol, into 200 cm^ of toluene and into 4.5 cm^ of triethylamine is bubbled hydrogen sulphide for 22 hours, the reaction mixture is poured on to a N aqueous solution of hydrochloric acid, the organic phase is separated by decanting, it is washed with water, it is dried and it is concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica eluting with a mixture of benzene -and ethyl acetate (8:2) and i crystallised from isopropyl ether and 18.5 g of 3-phenoxy I a-hydroxy benzene ethane thioamide are obtained, M.Pt. = r?0°C. 25 IR Spectrum (chloroform) Absorption at 3600 cm~"^ attributed to the free and associated OH. Absorptions at 3478, 3360 cm~^ attributed to - -Jo - 197175 Absorptions at 1670, 1578, 1477 cm attributed to the aromatic nuclei and to - C - NIL-, il 2 S NMR Spectrum (deuterochloroform) Peaks at 3-97 - 4.03 p.p.m., attributed to the hydrogen ^ of the hydroxyl, Peaks at 3-18 - 5-25 p.p.m., attributed to the hydrogen borne S by the carbon at a of Peaks from 6.92 to 7-58 p.p.m., attributed to the hydrogens of the aromatic nuclei, 10 Peak at 7-5 p.p.m., attributed to the hydrogens of the -NE^. Preparation 14: (2-phenoxy 4-thiazolyl) methanol. t Stage A: Ethyl £-£henoxz thiazol_e_4^carboxy l.a 7. 2 g of ethyl 2-chloro thiazole 4-carboxylate, 50 cur t. of dimethylformamide, 2.5 cnr of hexamethyl phosphorotri amide 15 and 1.5 g of sodium iodide are mixed, the reaction mixture is taken to 100°C, it is maintained for 1 hour at this temperature then cooled to 20°C, 1.32 g of potassium phenate ^ are introduced, in portions, the reaction mixture is taken to reflux for 1 hour 30 minutes, 0.66 g of potassium phenate are added, the refluxing is maintained for 1 hour 30 minutes, the whole is cooled, water and ethyl acetate are added, the whole is extracted with ethyl acetate, the organic phases are washed with water and they are concentrated to dryness, the residue is chromatographed on silica eluting 25 with a mixture of hexane, isopropyl ether and triethylamine (7:3:1) and 1.08 g of ethyl 2-phenoxy thiazole 4-carboxylate are obtained, M.Pt. = 67°C. .71 - 197175 Stage B: i.2j^henoxy_4^thiazolzll me^hanol^ Into a solution of 12 g of ethyl 2-phenoxy thiazole 4-carboxylate in 60 cm? of toluene are introduced, slowly, at -10°C, 54 cm^ of toluene solution of diethyl sodium aluminium hydride titrating 2 moles/litre. The whole is agitated for 1 hour at -5°C, 80 cm^ of a 2U aqueous solution of hydrochloric acid then water are introduced at -20°C, the insoluble matter formed is eliminated by filtration, the filtrate is decanted, the organic phase is' washed with water, with a 2N aqueous solution of sodium hydroxide, then with water and concentrated to dryness, the residue is chromatographed on silica eluting with a mixture of methylene chloride and ethyl acetate (8:2) and 8.15 g of (2-phenoxy 4-thiazolyl) methanol are obtained. IR Spectrum (chloroform) Absorption at 5590 cm-^" attributed to the hydroxyl, Absorptions at 1551, 1530, 1503, 1486 cm ^ attributed to the aromatic nucleus and to the thiazole, Absorption at 690 cm""^ attributed to the phenyl (deformation). NMR Spectrum (deuterochloroform) Peak at 4.5 p.p.m., attributed to the hydrogens of - 0, Peak at 3-5 p.p.m., attributed to the hydrogen of -OH, Peak at 6.66 p.p.m., attributed to the thiazolic hydrogen, Peaks from 7-10 to 7.50 p.p.m., attributed to the hydrogens of the aromatic nucleus. Preparation 15: (RS) a-cyano (2-phenoxy 4-thiazolyl) methanol. Stage A: £2^henoxy_4^thijizol;£l). methanal^ 197175 NHB Spectrum (deuterochloroform) Peak at 4.08 p.p.m., attributed to the hydrogen of the -OH, Peak at 5-4-1 p.p.m., attributed to the hydrogen of CH - OH, Peak at 7-33 p.p.m., attributed to the hydrogens of the phenyl, Peak at 7-0 p.p.m., attributed to the thiazolic hydrogen. Preparation 16 : 3-phenoxy 4-fluoro -methyl benzylic alcohol 15,8 cm3 of a 2,6M solution of methyl magnesium iodide in ethyl ether are added at 20°C' to a mixture containing 8 g of 3-(4-fluorophenoxy) benzaldehyde in 50 cm3 od ethyl ether. The mixture is maintained at ambiant temperature .during one hour, then is poured in an-aqueous solution of ammonium chloride, decanted, extracted with ethyl ether, the expected product is obtained and then is veristallized in isopropyl ether. M Pt : 64°C. Examples of Compositions. Example A: Preparation of a soluble concentrate. A homogenous mixture is made, consisting of: Product of Example 1 0.25 g Piperonyl butoxide 1 g Tween 80 0.25 g Topanol A *.... 0.1 g Water .... 98.4 g Example B: Preparation of an emulsifiable concentrate. Intimately mixed are: Product of Example 1 Piperonyl butoxide . Topanol A Xylene - 95-885 g 0.5 g 0.1 g 0.015 g c*«T - $K - 1971 Example C: Preparation of an emulsifiable concentrate. A homogeneous mixture is made, 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. Homogeneously mixed.are: Product of Example 1 0.25 g Tabu powder - . - • 25 g Cedar-needle powder - 40 g Pinewood dust 33-75 S Erilliant green * - 0.5 g p-Nitrophenol 0.5 g .1«./ / JL » O - 9^- Study of the activity of the compounds according to the invention on parasites. X* Example JL: Study of the lethal effect of the compounds of Examples 1 to 8 on house flies. 5 The test insects are female house flies of a strain sensitive to pyrethrinoids, raised at 22-23°G and 60-65% relative humidity and from 4 to 5 days old. Work is carried out "by topical application of^jil of acetonic solution to the dorsal thorax of the insects using the 10 Arnold micro manipulator. 50 individuals are used per dose of the product to be tested. The mortality check is carried out twenty-four hours after treatment. It is established that in the test used the products show good lethal activity. 15 Example jk: Study of the lethal effect of the compounds of Examples 1 to 8 on larvae of Spodoptera littoralis. The tests are carried out by topical application of an acetonic solution using the Arnold micro manipulator to the dorsal thorax of the larvae. 15 larvae are used 20 per dose of product to be tested. The larvae used are larvae in the fourth larval stage, that is to say about 10 days old when they are raised at 24°C and 65% relative humidity. After treatment the individuals are placed on an artificial nutrient medium (Poitout medium). 25 The mortality check is carried out 48 hours after treatment. rtt is established that, in the test used, the products <T' r r /> A rr^ 07^0) ft j i [1 f -if1} 3 1 Q'yi ^ ~ •+- v i -L i (J - - show good. Lethal activity. Example Study of the activity of the products of Examples 1 to 8 on larvae of Epilachna Varivestris. The tests are carried out by topical application 5 in a manner similar to that used for the flies and the larvae of Spodoptera. Larvae in the penultimate larval stage are used and, after treatment, the larvae are fed with bean plants. The mortality check is carried out 72 hours after treatment. 10 It is established that, in the test used, the products show good__J.ethal activity. Example Study of the knock-down activity on the house nz- The test insects are female house flies from 4 to 5 15 days old. Work is carried out by direct spraying in a Kearns and March cylinder, using as solvent a mixture of acetone (5%) auid Isopar L (petroleum solvent) (amount of solvent used 2 ml in one second). 50 insects are used per dose. Checks are carried out every minute up to 10 20 minutes, then at 15 minutes and the KT 50 is determined by the usual methods. It is established that the products show good activity and one of them, the product of Example 1, shows remarkable activity since its KT 50 is 0.4 minutes, 1.26 minutes and 25 2.02 minutes for respective concentrations of 1, 0.5 and 0.25 g/litre. 1 . .. ^ /> J] </div>

Claims

<div class="application article clearfix printTableText" id="claims"> ' ' . 197175 - 9* - Example Activity on Tetranychus Urticae. Adulticidal_ test^ Bean plants are used comprising two leaves which, are treated with a Fisher pistol at different doses of 5 the products to be tested. After drying these plants are infested at the rate of 25 females of Tetranychus Urticae per leaf and kept at 22-23°C and 60-65% permanent artifical relative humidity- The counts of the live and dead acaridae are carried out 24 and 48 hours after 10 treatment. The products of Examples 1 to 8 show good adulticidal activity in this test. s211 Example Study of the insecticidal activity, on Culex pipiens mosquitoes, of the compound of Example 1 used 15 in the form of a smoke-producing coil. Neutral supports of smoke-producing coils are impregnated with active substance in solution in acetone. 20 female mosquitoes , from 4 to 5 days old, are released into a closed glass cylinder of 13*50 dnr and for 2 minutes 20 a smoke-producing coil, burning at one end, is introduced. The knock-down check is carried out every minute and the test is stopped 5 minutes after all the insects have been knocked down. The results are as follows: 25 - at the dose of 0.60% by weight of active substance per coil the KT 50 is 5»42 minutes, - at this dose the lethal effect is 98.3%* I 97 1 / 5 IWHAT CLAIM " 1. Compounds of formula (I *) (I*) the Cycto#lcne.t-y IR,cts Siruciu-JH. / in which the double bond has the geometry represents: either an alkyl radical containing from 1 to 18 carbon atoms, or a benzyl radical (optionally substituted by one or more radicals selected from alkyl radicals containing from 1 to A carbon atoms, alkenyl Radicals containing from 2 to 6 carbon atoms, alkenyloxy radicals containing from 2 to 6 carbon atoms, alkadienyl radicals containing from 4 to 8 carbon atoms, the methylenedioxy residue and halogen atoms), or a group: CHjEJ t 3 o\ Si QC V Q~ < ■* (in which represents a hydrogen atom or a methyl radical and 1*2 represents a monocyclic aryl or a -CI^-C^CH group); 100 -J*r- -e nit i o t Jl £ or a group: (in which R^ represents an aliphatic organic radical containing from 2 to 6 carbon atoms nnri one or more carbon-carbon unsaturations) or a group: (in which R^ is as defined above and R'^ and R^* which may be the same or different, each represents 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 alkoxycarbonyl group containing from 2 to 5 carbon atoms or a cyano group), or a group: h o 1 i Q >y i *y r . 100 - ^ < 1 » t> (in which B represents a Cf^ or C=0 group or an oxygen r sulphur atom, R^ represents a hydrogen atom, a methyl radical a radical -C0NHo a radical -CSNH„ or a radical .-C~Oi 1 1 [-C-Ctjf, R represents a halogen atom or a methyl radical and n is 0, 1 or 2), or a group: H CE or a group: (in which the substituents R^, R-,, Rg and Rg each represents 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), / r\'l or a group: -ch2-n 3 10^ - >0^"*- -ch2-c=ch 1 Q 71 7 ~ JL «-> i* j. / o1 or a group: ^10 CH " HI1 " R12 (in which E1q represents a hydrogen atom or a CN radical, R12 rePresen'ts a -CHg- radical or an oxygen atom and R^ represents a thiazolyl or thiadiazolyl radical, I c10 the "bond with - CH - being found at any one of the available positions in R^ and R^ being bonded to R^ via the carbon atom between the sulphur atom and a nitrogen atom inRll>, or a group: 197175 !0t>- (in which. R^ represents a hydrogen atom or a CN radical ) or a group: (in which R,, is defined as above) or a group: (in which R represents a hydrogen atom or a methyl, ethynyl or cyano radical and R, _ and R,, are different ^15 lb and each represents a hydrogen, fluorine or bromine atom) or a group: i i i | ^ N.Z. PATEWT OFFlCgjjEj ' 14 MA* 1984 i f\, t*? A, — < 1 f u - lofrf- (in which R, . is defined as above and R,-, and R, Q, which 14 i / lo may be the same or different, each represents a hydrogen atom, 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 alkylsulphonyl group containing from 1 to 4 carbon atoms or a trifluoromethyl, 3,4-methylenedioxy chloro, fluoro or bromo group and B' represents an oxygen atom or a sulphur atom); and R represents a saturated or unsaturated, straight, branched or cyclic alkyl radical containing to 18 ca rbon a toms: in all their possible stereoisomeric forms, as well as mixtures of these stereoisomers. 2. Compounds as claimed in claim 1 of the formula (I): (I) die cyCcphasic morety » i in which the double bond has the geometry represents: either an alkyl radical containing from 1 to 18 carbon atoms, 10< - JjOtf - 1971? or a benzyl radical optionally substituted as defined in claim 1, or a group: (in which R^ and are as defined in claim 1), or a group; (in which R„ is as defined in claim 1), or a group: (in which R^} R'^ and R^ are as defined in claim 1), or a group: to10 - 197175 in which B, E^, and n are as defined in claim l), or a group: 5 or a group: -CH^— -7 100 - "s Q -s r ^ f _L £ (in which the substituents R^, R^, Rg, Rg and the symbol S/I are as defined in claim .1) or a group: ch2-n -rCH2-G=GH and R is as defined in claim 1. Compoimds as claimed—in claim 1 ur claim 2 in the cyclnpropanjLc acid moiety is of lR,cis or 1R,trans structvree. . dcusn I or cLa-ur\ "5 3 4. Compounds as claimed in pny one of claims 1 tu 3^ in which R represents a methyl radical. Cta~r> I -I Compounds as claimed in /any one of claims- 1 feo 3 in which R represents an ethyl, n-propyl, isopropyl, tertbutyl or cyclopropylmethyl radical. St. ir group of formula q-1 Compounds as claimed in any one of claims 1 to % of /-) in which A'^represents a 5-benzyl-3-furylmethyl group, a (in which R^ represents a -CH2-CH=CH2, -Cf^-C^CH-CH^, -CH2-CH=CH-C2H5 or -CH2-CH=CH-CH=CH2 radical) or a 3-phenoxybenzyl, a-ethynyl-3-phenoxybenzyl, 3-benzoylbenzyl, 197 17b - 108 - 1- (3-phenoxyphenyl) -ethyl or(j( -thioamido-3-phenoxybenzyl group. 6. Compounds as claimed in any one of claims 1 to 5 in which A' or A represents the (4S)3-methyl-2-(2-propenyl) -1-oxo-cyclopent-2-en-4-yl group, the (1,3,4,5,6,7-hexahydro- I,3-dioxo-2H-isoindol-2-yl)-methyl group, the (RS)cyano-(6-phenoxy-2-pyridinyl)-methyl group, the [5-(benzyl)-3-furanyl]methyl group, the 1-(3-propargyl-2,5-dioxo-imi-dazolidinyl)-methyl group or the (R)1-(3-phenoxyphenyl)-ethyl group. 7. (1S)2-Methyl-4-oxo-3-(2-propenyl)-2-cyclopenten-1-yl (1R,cis)2,2-dimethyl—3[(Z)-3-methoxy-3-oxo-1-propenyl]-eyelopropane-carboxylate. 8. 1-(3-Propargyl-2,5-dioxo-imidazolidinyl) -methyl (lR,cis)-2,2 - dimethyl-3 £"(Z) -3-tert*-butoxy-3-oxo-l-propenyi] - cyclopropane-carboxylate. 9. 1-(3-Propargyl-2,5-dioxo-imidazolidinyl)-methyl (1R, cis)2,2-dimethyl-3-[(Z)-2-cyclopropylmethoxy-carbonyl-ethenyl]-cyclopropane-carboxylate. 10. 1 (R) 1-(3-Phenoxyphenyl)-ethyl (1R,cis)-2,2-dimethyl-3-[ (Z)-2-isopropoxycarbonylethenyl]-cyclopropane-carboxylate. II.1- (3-Propargyl-2,5-dioxo-imidazolidinyl)-methyl (1R,cis) -2,2-dimethyl-3-[(Z)-2-isopropoxycarbonylethenyl] - cyclopropane-carboxylate. 12 . 1- (3-Propargyl-2,5-dioxo-imidazolidinyl)-methyl (1R,cis)-2,2-dimethyl-3-[(Z)-2-isopropoxycarbonylethenyl]-cyclopropane-carboxylate. 13. (RS)ef-cyano- (3-benzoylphenyl)methyl (1R,cis^ z) 2 ,2-dimethyl-3-(3-methoxy-3-oxo-1-propenyl)cyclopropane-1-carboxylate, 14 Compounds as claimed in claim 1, other than those claimed in any one of claims 7 to 12 as herein specifically 197175 % ilf. w>cl ^ disclosed in any one of Examples 1 to J&ft. i5" Mf. Compounds as claimed in claim 2, other than those 7 & & claimed in any one of claims f> to JWf as herein specifically £x^cL*Y\j>le.S disclosed in any one of [Example 1 to 8. iff. A process for the preparation of compounds of formula (I') as defined in claim 1 which comprises reacting an acid of formula (II), CH CH ho-c II 0 (II) tAe cyJ-opropose ncety » i (in which the double bond has the geometry Z^fand R is as defined in claim 1), or a functional derivative of this acid, with an alcohol of formula (III), A'OH (III) im '7-13. A process for the preparation of compounds of (in which A' is as defined in cla: formula (I') as defined in claim 1 which comprises esteri-fying a compound of formula (VIII), ho2c (viii) -f <"> (•;' .t. : 11 ~ 1 i X i C> |0 - 109 - che cy doprt>i>r<^ie mtrtdC^ & °$ as zcructustr (in which^A' is as defined in claim 1) with an appropriate esterification agent serving to introduce the group R. n A process as claimed in claim Js8 wherein the compound of formula (VIII) is prepared by jcajtcfuf hydrogenation of a compound of formula (XI), ho2c-c=c, (xi) the ctjolcpftrpasie McneCij (O ^ c*S ctsicJ (wherein^A* is as defined in claim 1). A process for the preparation of compounds of formula (i1) as defined in claim 1 which comprises refill 1;/ hydrogenating a compound of formula (XII), ro2c-csc (XII) the: o»j(Jopropct-^ie- /Yicne-ty M stfu.cJxc/T*~ (wherein^A' and R are as defined in claim 1) whereby the desired compound of formula (I') is obtained. A process as claimed in claim 2Q wherein the compound of formula (XII) is obtained by esterification of a iff compound of formula (XI) as defined in claim with an appropriate esterification agent serving to introduce the group R. 97175 - iiV - 3.1 ig ^2. A process as claimed in claim J-9' or claim ^2-f wherein the compound of formula (XI) is obtained by reaction of a compound of formula (X), c13c-ch2-02c-c=c / nl coo-a-' (x) the ujotoprvpasu? menety *o //?, c<S zGruc-tuS& cist c/ (wherein^A' is as defined in claim 1) with an. agent capable of cleaving selectively the ester function borne by the acetylenic carbon atom. 7 a i A process as claimed in claim wherein the compound of formula (X) is obtained by reaction of a compound of formula (IX), Cl_C-CHo-0^C-C=C J L £. ~ (IX) Cwheszcn the OLjtJopropcisne _rnoietj ^ l#,<us StrucJu^G: ) (£ ^with an alcohol of formula (III) as defined in claim 2. 3 -24". A process for the preparation of compounds as claimed in claim 1 substantially as herein described. "Mf-2-5. A process for the preparation of compounds as claimed in claim 1 substantially as herein described in any one I if ___ - cu>d 16 to 88. of Examples I to r4 APR 1984 197175 -112- 1 2£> A process for the preparation of compounds as claimed in claim 2 substantially as herein described in any one of Examples 1 to 8. 26. A process as claimed in claim 1$ for the preparation of compound as claimed in claim 2. 27. Compounds as claimed in claim 1 whenever prepared by a process as claimed in any one of claims 16 to 24. 28. Compounds as claimed in claim 2 whenever prepared by a process as claimed in claim 25 or claim 26. 29. A modification of a process as claimed in any one of claims 16 to 22, for the preparation of the compound claimed in claim 13, wherein R is replaced by an (RS)o<-cyano-(3-benzoylphenyl)methyl group. 30. A process, for the preparation of the compound as claimed in claim 13 substantially as herein described in Example 15. 31. The compound claimed in claim 13 whenever prepared by a process as claimed in claim 29 or claim 30. 32. Compositions for the control of pests of plants, domestic pests and pests of warm-blooded animals characterised in that they contain at least one compound as claimed in any one of claims 1 to 15. 33. Insecticidal compositions containing, as active ingredient, at least one compound as claimed in any one of claims 1 to 15. 34. Insecticidal compositions containing, as active, ingredient, at least one compound as claimed in any one of claims 7 to 12. ^ ^ 35. Animal feedstuffs containing at least one compound as claimed in any one of claims 1 to 15. 36. Insecticidal, acaricidal or nematocidal compositions comprising at least one compound as claimed in any one of claims 1 to 15 in association with at least one pyrethrin-oid ester selected from the esters of allethrolone, of 3,4 , 5,6-tetrahydrophthalimido-methyl alcohol, of 197175 -113- 5-benzyl-3-furyl-methyl alcohol, of 3-phenoxybenzyl alcohol and of a-cyano-3-phenoxybenzyl alcohol with chrysanthemic acid, by the ester of 5-benzyl-3-furyl-methyl alcohol with 2,2-dimethyl-3-(2-oxo-3-tetrahydrothiophenylidene-methyl)-cyclopropane-1-carboxylic acid, by the esters of 3-phenoxybenzyl alcohol and of a-cyano-3-phenoxybenzyl alcohol with 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylic acid, by the ester of a-cyano-3-phenoxybenzyl alcohol with 2,2-dimethyl 3-(2,2-dibromovinyl)-cyclopropane-1-carboxylic acid, by the ester of 3-phenoxybenzyl alcohol with 2-parachlorophenyl-2-isopropyl acetic acid, by the esters of allethrolone, of 3,4,5,6-tetrahydrophthalimidomethyl alcohol, of 5-benzyl-3-furyl-methyl alcohol, of 3-phenoxybenzyl alcohol and of a-cyano-3-phenoxy-benzyl alcohol with 2,2-dimethyl-3-(1,2,2,2-tetrahalo)-cyclopropane-1--carboxylic acids, in which "halo" represents a fluorine, chlorine or bromine atom, it being understood that the compounds of formula (I') can exist in possible stereo-isomeric forms as can the acid and alcohol moieties of the pyrethrinoid esters above. 37. Pharmaceutical compositions comprising, as active ingredient at least one compound as claimed in any one of claims 1 to 15 in association with a carrier or excipient. 38. Insectidal, acaricidal, nematocidal and antiparasite compositions substantially as herein described in any one of Examples A to D. 39. A method of combatting insects, acarids and/or nematodes which comprises applying to a site other than a human body infested 19717b 114 with or susceptible to infestation by insects, acarids and/or nemadtodes an effective amount of a compound as claimed in any one of claims 1 to 15. 40. A method as claimed in claim 39 substantially as herein described. 41. A compound of formula wherein the cyclopropane moiety is of IR, cis structure and co2A- (VIII) A' is as defined in claim 1 with the proviso that when A' is alkyl it contains 9 to 18 carbon atoms. '77 n* - 115 - 42. A compound of formula hojc-c-c (XI) wherein the cyclopropane moiety is of IR, cis structure and A* is as defined in claim 1 with the proviso that when A* is alkyl it contains 9 to 18 carbon atoms. 43. a compound of formula ro2c-cec co2a' (xii) wherein the cyclopropane moiety is of IB, cis structure and R and A' are as defined in claim 1 with the proviso that when A' is C1_8 alkyl R represents a saturated or unsaturated straight branched or cyclic alkyl radical containing 9 to 18 carbon atoms. ROUSSEIj—uclaf </div>