CYCLOPROPAN CARBOXYLSAEURE DERIVATIVES, YOUR PRODUCTION AND APPLICATION WITH THE FIGHT AGAINST PARASITS AGAINST PLANTS, ANIMALS AND RESTAURANTS, YOUR COMPOSITIONS AND INTERMEDIATE PRODUCTS.

Novel

cyclonropane

carboxylic acid derivatives, their preparation, their

apolication

to the control of harmful plants, of animals and boulders, compositions comprising them and the novel

intermédiaries

obtained.The present invention relates to novel derivatives of cyclopropane

carooxylîque

, their preparation, their application to the control of parasites in plants, animals and premises, compositions containing them and intermediates obtained.The invention concerns under 'all the possible isomeric forms or as mixtures, the compounds of formula (I-') emi1.1 wherein A ' represents - either an alkyl radical containing from 1 to 18 atoms because Bone Morphogenic.- either a benzyl radical optionally substituted by one or more radicals selected from the group consisting of alkyls having from I to 4 carbon atoms, alkenyl radicals having from 2 to 6 carbon atoms, alkenyloxy radicals having from 2 to 6 atoms because Bone Morphogenic, radicals having from 4 to 8

alcadiényles

carbon atoms, methylene dioxy radical and the atoms

dthalo

gene, - either a groupementemi2.1 wherein the substituent r1 represents

dthydro

- gene or a methyl radical and 12 r2 substituent group or a cyclic mono-aryl - ch2 CCH and especially a group 5 benzyl 3-furyl-methyl, - either a group emi2.2 wherein a represents a hydrogen atom or a methyl radical and r3 represents an aliphatic organic radical having 2 to 6 carbon atoms and one or more in-store-carbon-carbon and especially the radical - ch2 CH-ch2, - ch2 CH-ch ch3, - ch2 CH-ch ch ch2, - cn2 Ch=ch ch2-to-ch3, - either a groupementemi2.3 wherein a represents a hydrogen atom or a methyl radical, r3 retains as defined hereinbefore, the R '1 and R' 2, identical or different, represent a hydrogen atom, a halogen atom, an alkyl radical containing 1 to 6 carbon atoms, an aryl radical having from 6 to 10 carbon atoms, a group having from 2 to 5

alcoyloxycarbonyle

carbon atoms, or a cyano group, - either a groupementemi3.1 wherein 3 represents an oxygen or sulfur or a groupementemi3.2 r4 - and-or ch2 represents a hydrogen atom, a radical - c - n, a methyl radical, a radical - CO, radical or a radical -

CSNH2

- ch-C., r3

repréesente

a halogen atom or a radical

néthyle

and n represents a number equal to 0, 1 or 2, and particularly the group 3-phenoxy - Bas

zyle

, -cyano 3-phenoxy benzyl, alpha-ethynyl 3-phenoxy benzyl, 3 benzoyl-benzyl, from 1 - (3 phenoxyphenyl) ethyl α or; -

thioamido

3-phenoxy benzyl, either an emi3.3 groupementemi3.4 - either a wherein the substituents R6, and R7, and R8, r9 represent a hydrogen atom, a chlorine atom, or a methyl radical and wherein s/i symbolizes an aromatic ring or a ring like dihydro or tetrahydro tetrahydro, - either a groupementemi4.1 - either an emi4.2 wherein r10 represents a hydrogen atom or a radical is, represents a radical - r12 ch2 - or an oxygen atom, represents thiazolyl or IIR

thiadiazolvle

whose binding avecemi4.3 could be located on any available positions, being bound to r12 r11 via the carbon atom between the sulfur atom and a nitrogen atom, or a - groupementemi4.4 - either a groupementemi4.5 wherein r13 represents a hydrogen atom or denoting an NC callus, - either a ou pementemi4.6 wherein r13 is defined as above, and the radical Bas

zoyle

is in position 3 or 4, wherein either a - groupementemi5.1 r14 represents

dthydrogène

, methyl, ethynyl or cyano and r15 and R16, different, represent

dthydrogène

, fluorine or bromine, - either unemi5.2 wherein r14 is defined as above, each of the r17 independently represents an alkyl group containing 1 to 4 carbon atoms, alkoxy having 1 to 4 of carbon atoms, alkylthio of 1 to 4 containing carbon atoms, alkyl having from 1 to 4 aromatic sulfonyl carbon atoms, trifluoromethyl, 3.4 to-methylene methylenedioxy, chlorine, fluoro or bromo, P represents a number equal to 0, 1 or 2 and b ' represents an oxygen atom or a sulfur atom and R represents alkyl containing I to 18 carbon atoms substituted with one or more functional groups which are identical or different, or an aryl group containing 6 to 14 carbon atoms optionally substituted by one or more identical or different functional groups, or heterocyclic group optionally substituted by one or more identical or different functional groups, compounds in which the double bond at the geometry Z or E.The compounds of formula (I-') can exist in many forms stereoisomers: they possess in effect two asymmetric carbons in 1 and 3 cyclopropane; they pre feel also isomerism e/z at the double bond; they may, moreover, have one or more centers of asymmetry in the a portion as in the R portion.When A ' represents alkyl, it is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or

terbutyle

.When A ' represents a benzyl radical substituted with one or more alkyl radicals, it is preferably methyl or ethyl radicals.When A ' represents a benzyl radical substituted with one or more alkenyl radicals, these are preferably vinyl radicals, allyl, 2 a-methylallyl, or isobutenyl.When A ' represents a benzyl radical substituted with one or more

alcéy

-to-

loxv

, is preferably the radical a vinyloxy, allyloxygroups, 2 a-

méthylallyloxyisobutény

or far.When A ' represents a benzyl radical substituted with one or more halogen atoms, it is preferably chloro, bromo or fluoro.When R is an alkyl radical substituted with one or more functional groups, is meant preferably by alkyl radical containing 1 to 8 carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl or tertbutyl.When R is an alkyl radical substituted with one or more functional groups, is meant preferably by functional group, a halogen atom, OH or SH, a group origins or SR 'in which R' represents an alkyl radical containing 1 to 8 carbon atoms, a group no2 ouemi6.1 wherein R "and R" ' > identical or different represent a hydrogen atom, or an alkyl radical containing 1 to 8 carbon atoms, a group c - n, So 3h or p04h2 or a group

COalc1

,

SO2alc2

, or so3alc3 in which alk1, alc2 and alc3 represent alkyl radicals containing I to 18 carbon atoms.R may also represent an alkyl radical substituted by an aryl radical as

exenple

by the benzyl radical or the radical phenethyl,

érentuellement

itself substituted by one or more OH groups, or alk 1 containing

Oalc

to 8 carbon atoms, more groups if a by a CF3, OCH3, CFS3, or by a (grams)

groupmentEMI7.1

R can be alkyl substituted also in on two adjacent carbons by a group (g1)

EMI7.2

the Cu substituted groupementemi7.3When R is an alkyl radical substituted with one or more functional groups -

ün

, it may be mentioned as preferred values of R radicals (ch2) n - chal3 wherein n is an integer from 1 to 8 and Hal is a halogen atom, for example the radical - ch2-to-ccl3, - ch2-to-cf3, - ch2-to-ch2-to-ccl3 or - ch2-to-ch2-to-cf3, an n - (ch2), HM - hal2 wherein hal is as defined above and NL is a number O! 8, for example the radical - ch2-to-chcl2 ch2-to-chf2 - CHF2 or - or, - n ch2 (ch2)Hal-wherein n and Hal are defined as RO des addition, for example the radical - ch2-to-ch2cl ch2-to-ch2f - or, - - C. (

CHal

) wherein hal is as defined above,

parEMI7.4

Emi8.1 (ch2)- or n-CN, wherein n is defined as précédemment, emi8.2 wherein hal is as defined above, for example the radicalemi8.3 The 5 - (ch2) n gold ', wherein n is defined as above and R' represents a hydrogen atom or an alkyl radical Liné CNC area or branched, having 1 to 8 carbon atoms, for example the radical - ch2-to-och3, - ch2-to-ch2 O-ch3, - ch2-to-ch2 O-ch2-to-ch3 or ch2-to-ch2 OH -, 10 - (ch23n emi8.4 wherein n and RT are defined as above and the two radicals R ' may be different from one another, for example the radicalemi8.5Emi8.6 ouemi8.7Emi8.8 wherein n is defined as 15 previously, e.g. the radicalemi8.9Emi8.10, wherein n is as defined above, for example the radicalemi8.11Emi8.12 wherein n is as defined above, for example the radicalemi9.1Emi9.2 wherein nis as defined hereinbefore, for example the benzyl radical or phénéthyle, emi9.3 wherein n is as defined above, for example the radicalemi9.4When R represents an optionally substituted aryl radical, it is preferably phenyl or phenyl substituted by one or more OH groups, or alk

Oale

, containing 1 to 8 carbon atoms, or a group CF3, ocf3 scf3 or when R represents a heterocyclic radical, it is preferably pyridinyl, furanyl, phenyl - thiourea, oxazolyl or thiazolyl.The invention particularly relates to compounds of formula (I-'), as defined above, having

àEMI9

. - 5 wherein a represents either an alkyl radical containing from 1 to 18 carbon atoms, a benzyl radical or - optionally substituted, as defined above, or a groupementemi9.6 - wherein the substituents are defined as r1 r2 and previously, - either a groupementemi9.7 r3 wherein a and are as defined above, - either a groupementemi10.1 wherein A, the R '1 @ the R' 2 and r3 are defined as above, - soitemi10.2 wherein b represents an oxygen atom, a groupementemi10.3 the CH2 - or -, ?.4 is defined as précédemment, r5 represents a chlorine atom or a methyl radical and n is a number equal to 0, 1 or 2, and particularly the group 3-phenoxy benzyl, α-cyano - 3-phenoxy benzyl or ethynyl

3phénoxybenzyleJ

- either a groupementemi10.4 - either a groupementemi10.5 - either a groupementemi11.1 wherein the substituents R6, and R7, and R8, r9 and s/i are as defined above, - either a groupementemi11.2 and R is defined as above.The invention particularly relates to compounds of formula (3!) for which the double bond at 12 Z-geometry.Among the preferred compounds of the invention, include the compounds wherein the coupling the cyclopropane because that e

culièrement

those for which the coupling the carboxylic acid I - do

cyclopropa

1r cis-structure is.The invention particularly relates to compounds of formula (I-') as defined previously, whereina represents an α-cyano 3-phenoxy benzyl as e, R or R as well as those in which A' represents a group 2-methyl 4 oxo-3 (2 a-propenyl) 2 a-cyclopenten1-yl form e, R or R.The invention especially relates to the compounds of formula (I-') for which R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted with one or more functional groups, and especially those in which R is an alkyl radical substituted with one or more halogen atoms, such as one or more fluorine atoms. Examples of alkyl radical substituted with one or more halogen atoms, include especially the radical - is CH2CF3.The invention especially relates to the compounds whose preparation is further explained below in the experimental part and in particular, among them, the compounds of examples 1, 2, 23, 26, 29, 30 and 35.The compounds of formula (I-') have interesting properties which enable their use in pest control, it may be for example of combating plant pests, parasites premises and parasites from warm-blooded animals. C1 is thus usable products according to the invention for combating insects, nematodes and parasitic mites of plants and animals.The invention has for its object to the use of compounds of formula (I-') for combating plant pests, parasites premises and animal parasites to

sanr

hot.The products of formula (I-') may thus be used especially for insect control in the agricultural sector, for example for fighting against aphids, the cabbage and beetles. They are used mock doses thereof between 10 g and 300 g of active material per hectare.The products of-formula (I-') can also be used s for combating insects in the premises, for fighting a flies, mosquitoes and cockroaches.The compound of the example 1 is an extremely remarkable as shown by the test results below.n has excellent lethal and a very good level of knock-down syndrome.The products of formula (F.) are more stable and are not toxic to mammals.All of these properties to products of formula (I-') products that are ideally suited to the requirements of the modern agrochemical industry: they allow - protect crops while preserving 1' environment.The products of formula (I-') may also be used to control mites and nematodes

parasi

tees plants.The compounds of formula (I-') can also be used to control mites parasitic on animals, to control for example against ticks and especially ticks of the species

Boophilus

, those of the species

Hyalomnia

, those of the species

Amblyomnia

and those of the species

Rhipicepha

- read, or to combat all sorts of gall and especially the scabies, the mange and scabies

chorioptique

.The invention therefore also relates to the compounds ing for the control of parasites in warm-blooded animals, pests premises and plants, characterized in that they comprise at least one of the products defined above.The invention has for its object the insecticidal compositions containing as active ingredient at least 1' a products defined above.Among the compositions particularly insecticides

préfé

- lengths of the invention, it may be mentioned in particular to compositions containing the (cis-1r) 2.2-to-dimethyl 3/(Z-) 3 (2.2.2-a trifluoroethoxy) 3 oxo 1 a-

propenyl

/cyclopropane carboxylate of (e) α-cyano 3-phenoxy benzyl, the (cis-1r) 2.2-to-dimethyl 3/(Z-) 3-oxo-substituted 3 - (or 2 - (1.1.1.3.3.3-to-hexafluoropropylene) propoxyl)/

1propényl

cyclopropane carboxylate of (e) α-cyano 3-phenoxy benzyl, the (cis-1r) 2.2-dimethyl 3|(a Z) 3-oxo-substituted 3 - (2.2.2-a-trifluoro ethoxy) 1 a-propenyl/cyclopropane carboxylate of (R-) has-ethynyl 3-phenoxy benzyl, the (cis-1r) 2.2-to-dimethyl 3/(Z-) 3-oxo-substituted 3 - (2.2.2-a-trifluoro ethoxy) 1 a-propenyl/cyclopropane carboxylate of (R) a cyano 6-phenoxy 2 and the pyridyl-methyl, the (cis-1r) 2.2-to-dimethyl 3/(Z-) 3-oxo-substituted 3 - (2 fluoro ethoxy) 1 a-propenyl/cyclopropane carboxylate of (e) a U-cyano-benzyl 3-phenoxy, the (cis-1r) 2.2-to-dimethyl 3/(Z-) 3-oxo-substituted 3 - (2.2.2-a-trifluoro ethoxy) 1 a-propenyl/cyclopropane carboxylate of (3 propargyl 2.5 a-

dioxoimidazolidinyl

) methyl, the (cis-1r) 2.2-to-dimethyl 3/(Z-) 3-oxo-substituted 3 - (2.2.2-a-trifluoro ethoxy) 1 a-propenyl/cyclopropane carboxylate of (1s) 2-methyl - 4 oxo - 3 and (2 a-

propenyl

) 2 a-Cyclopent I-yl.These compositions are prepared according to conventional methods for industry agrochemical or veterinary or industry products for animal nutrition.In these compositions for agricultural usage and premises, the active materials can other summed optionally one or more other pesticidal agents. These compositions may be in form of powders, granules, suspension, emulsion, solution, solutions for aerosols, strips fuels, bait or other preparations traditionally employed for the use of such compounds.In addition to the active ingredient, the compositions comprise, in general, a vehicle and/or a surfactant, nonionic, providing, further, a uniform dispersion of substances. the mixture. The vehicle used may be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, mineral oil, animal or vegetable, a powder such as talc, clays, silicates, the

kieselJhr

or solid fuel.The insecticidal compositions according to the I,

nvenXion

preferably contain 10% to 0,005% by weight of active material.According to an advantageous procedure, for use in the premises, the compositions of the invention are used as compositions

fumigantes

.The compositions of the invention can then advantageously be made, for the inactive portion, an insect coil, (or coil) fuel, or a noncombustible fibrous substrate. In the latter case, the fumigant obtained after incorporation of the active material is placed on a heating apparatus such as a

électromosquito

DDH.In the case of employing an insect coil, the inert support can be, for example, pyrethrum marc compound,

Tabu

powder (or

MachilusThumbergii

leaf powder), pyrethrum stem powder, cedar leaf powder, wood powder (such as pine sawdust) starch and powder of coconut shell.The dose of active material can then ' TREs, for example, of 0.03 to 1% by weight.In the case of employing a noncombustible fibrous carrier, the dose of active material can then be, for example, of 0.03 to 95, by weight.The compositions of the invention for use in the premises may also be obtained by preparing an oil-based sprayable active principle, this oil soaking up the wick of a lamp and then being subjected to combustion.The concentration of the active ingredient incorporated into the oil is, preferably, of 0.03 to 95% by weight.The insecticidal compositions according to the invention, since the compositions acaricides and nematicides may other summed

évenvuellement

of one or more other pesticidal agents. Acaricidal and nematicidal compositions can be in the form of powder, granules, suspension, emulsions, solution.For use acaricidal, are a preferred wettable powders, for foliar spray, containing 1 to 80.4 ' or liquids for foliar spray containing I to 500 g/l of active ingredient. There can further be used dusting powders containing 0.05 to 3% foliar active material.For use nematicide, preferably liquids used for soil treatment containing 300 to 500 g/l of active ingredient.And nematicidal acaricidal compounds of the invention are used, preferably at doses between I and 100 g of active material per hectare.To enhance the biological activity of the products of the invention can be admixed with synergists employed conventional in such a case such as the 1 - (2.5.8-to-trioxadodecyl) 2 propyl 4.5 to-methylenedioxy benzene (or piperonyl butoxide) or n - (2-ethyl hepyl) bicyclo-/ 2.2 - 1/5 and 3

heptène2,

di

carboximide

, or piperonyl-bis 2 - (2' n-butoxy-ethoxy) ethylacetal (or

tropital

).In the case of combating parasitic mites of animals, incorporated very often the products of the invention in food compositions in combination with a nutrient mixture adapted to animal feed. The mixture

nutritiel

may vary according to the animal species, that may incorporate cereals, sugars and grains, soya bean, peanut and sunflower, flours of animal origin, e.g. fish flours, synthetic amino acids, mineral salts, vitamins and antioxidants.The invention thus relates to the food compositions defined above.The compounds of formula (I-') have excellent general tolerance, and the invention therefore also relates to the products of-formula (I-'), as medicaments, for fighting against diseases caused by ticks and gall.The medicines of

l1invention

may other used both in human and veterinary medicine.The medicaments of the invention are particularly useful in human medicine for lice preventively or as against scabies. They can also be used as

anthelminitques

.The medicaments of the invention can be administered externally, by spraying, by

shampoor

, by bath or painting.The medicines for veterinary use may also be delivered by.the back

épince

swabbing the method termed method "for on earth". They may be also administered parenteral.The invention has for its object to Celtic Pharma S. compositions containing as active ingredient at least one of the medicaments defined above.Can also indicate that the products of the invention can be used as biocides or growth regulators.The invention also relates to the associations activity.in insecticidal, acaricidal or nematicidal, characterized in that they contain as active material, on the one hand at least one of compounds of general formula (I-'), and on the other hand, at least a

pyréthrinoldes

esters selected from the group consisting of esters of

alléthrolones

, alcohol 3.4.5 and 6 a-tetrahydrophthalimido methyl, 5 benzyl alcohol 3-furyl-methyl, alcohol 3-phenoxy benzyl alcohols 3-phenoxy-cyano-benzyl

chrysanthémiques

acids, esters 5 benzyl alcohol 3-furyl-methyl 2, 2diméthyl acids from 3 - (2 oxo 3 a-

tétrahydrothiophénylidèneméhyl

) cyclopropane 1-carboxylic acids, esters of alcohol 3-phenoxy benzyl alcohols and α-cyano 3-phenoxy benzyl 2, 2diméthyl acids from 3 - (2, 2 a-

dichlorovinyl

) cyclopropane 1 a-

carboxylisues

,

d'alcoolsa

-cyano-esters 3-phenoxy acid benzyl 2.2-to-dimethyl 3 - (2.2 to-

dibromovinyl

) cyclopropane 1-carboxylic acids, esters of alcohol 3-phenoxy benzyl acids 2 to-

parachlorophényl

2-isopropyl-acetic acids, esters of

alléthrolones

, 'd 'alcohol 3.4.5.6-to-

tétrahydrophtalimidométhylique

, 5 benzyl alcohol 3-furyl-methyl, benzyl alcohol

3phénoxy

α and alcohols; a cyano - 3-phenoxy benzylic acids 2.2-to-dimethyl 3 - (1.2.2.2-to-tetrahalo ethyl) or cyclopropane - 1-carboxylic acids, wherein "haloalkyl" represents fluorine, chlorine or bromine, it being understood that the

cQmposés

(I-') may exist in all their possible isomeric forms

séréo

- Copula model as well as the acids and alcohols esters

pyréthrinoides

above.The combinations according to the invention have in particular the interest or it allows combat, by the versatility of their action, a range of pests, wider, or exhibit unacceptable, in some cases, a synergistic effect.The invention also relates to a process for preparing the compounds of formula (I-'), characterized in that comprises reacting an acid of formula (III) in which R retains

EMI17.1

as defined hereinbefore, or a functional derivative of this acid, with an alcohol of formula (II) has' the OH (lil) wherein A'. retains the mimics defined hereinbefore, to obtain the compound of formula (I-') corresponding.The functional derivative of the acid used is preferably a diacid chloride.Are obtained by reacting the acid of formula (III), on the alcohol of formula (II) is carried out preferably in the presence of dicyclohexylcarbodiimide.The invention also relates to a process for the preparation as defined above, characterized in that the compound of formula (III) is prepared by subjecting within an organic solvent, a compound of formuleemi18.1 as trans or cis-in the lactone form, to the action of a compound of formuleemi18.2 wherein R retains its previous meaning, to obtain the compound of formula (ll) correspondantemi18.3 as a mixture of e and z isomers, are separated, if desired, in each of the isomers.In a preferred embodiment, the solvent used is selected from the group consisting of ethyl ether, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dimethoxyethane, alkanols, the diethylene glycol methyl ether and diethylene glycol diethyl ether.The compound of formula (b2) is prepared by the reaction of a compound of formuleemi19.1Hal representing a halogen anion, on a strong base. As strong base may be used for example a hydride, an amide, or an alkali metal alkoxide, or a

alcqyllithien

.The invention also relates to a process for the preparation as defined above, characterized in that the compound of formula IIC) is prepared by reacting a compound of formula (VI) wherein Hal emi19.2 represents a halogen atom and alk represents an alkyl radical containing from 1 to 20 carbon atoms, in a first step with an alkali agent capable of tearing the halogen atoms and then, in a second time, - either with an agent capable of introducing the carboxylic group to obtain the compound of formula (V-)

EMI19.3

which is subjected to the action of an esterification agent, pouremi19.4 wherein R retains the

mtme

defined hereinbefore - either with a derivative of formula Hal-- c02-R wherein Hal represents a halogen atom and R retains its previous meaning, to directly obtain the compound of formula (you) emi20.1 then subjecting the compound of formula (IV) to the action of a hydrogenating agent ménagée1 to obtain the compound of formula (VIII)

EMI20.2

wherein the double bond at the Z-geometry, which is subjected to the action of an acid capable of hydrolyzing agent selectively cleave the ester function on the carbon in the cyclopropane 1, to obtain the compound of formula (ll) corresponding.In a preferred embodiment of the above method, - Hal is bromine or chlorine, represents a radical - alk - L-

terbutyle

'alkaline agent capable of tearing the vinyl is butyllithium. halogens, - I' agent capable of introducing the carboxylic group is carbon dioxide, the L - 'provided hydrogenating agent is hydrogen in the presence of a palladium catalyst corm presence of traces of quinoline, - I' acid capable of hydrolyzing agent selectively cleave the ester function co2alc is paratoluene sulfonic acid.The method also includes a variant evident to the chemist in which the compound of formula (V-) is firstly subjected to the action of a hydrogenating agent

menagée

and in the second place to the action of a reducing agent.The invention therefore also relates to a variant of the method as defined above, characterized in that the first subjected the compound of formula (V-) to the action of a hydrogenating agent provided to obtain the compound of formula (VIII-) emi21.1 wherein the double bond in the Z-geometry, which is subjected to the action of an esterification agent, to obtain the compound of formula (VIII) correspondantemi21.2 wherein - R retains its previous meaning, and continues the synthesis as described above.The above method has obvious second variant, wherein the order of certain stages is modified.The invention therefore also relates to a method as defined above, characterized in that a compound of formula (IV)

EMI21.3

wherein R and alk, are defined as above, to the action of a hydrolyzing agent acid capable selectively cleave the ester function in 1 cyclopropane, to obtain the compound of formula (IX-)

EMI22.1

wherein R is defined as above, that - is subjected, where appropriate in the form of a functional derivative, to the action of an alcohol of formula (II) (lll)

A'

OH wherein A' retains the same meaning as before, to obtain the compound of formula I (X-)

EMI22.2

wherein R and a 'are as defined previously, which is subjected to the action of an agent except

hydrogéna

- provided, to obtain the compound of formula (I-'), - either the first subjected to the action of a hydrogenating agent provided, to obtain the compound of formula (ll)

EMI22.3

wherein R is defined as above and the double bond at the Z-geometry, and then, where appropriate in the form of a functional derivative, to the action of an alcohol (II), to obtain the compound of formula (I-').Preferential conditions for carrying out the method above are identical to those which have been previously defined for the like operations.The invention also relates to a process for preparing the compounds of formula (I-'), characterized in that a compound of formula (XL)

EMI23.1

wherein the double bond at the Z-geometry, to the action of an esterification agent, to obtain the compound of formula (I-') corresponding.In a preferred embodiment of the above method, the esterification is carried out with a functional derivative of alcohol, i.e. a derivative of n, n1:

diisopropylurée

formuleemi23.2 ofThe invention also relates to a method as defined above, characterized in that the product of formula (XII) is prepared by subjecting an acid of formula (V-)

EMI23.3

wherein alk represents an alkyl radical containing from I to 8 carbon atoms, to the action of the 2.2.2-to-trichloroethanol to obtain the compound of formula (XIII) emi23.4 which is subjected to the action of an acid hydrolysis agent to obtain the compound of formula (XIII-)

EMI24.1

which is subjected to the action of an alcohol of formula (II) (lll)

A'

OH wherein A' retains as defined hereinbefore, to obtain the compound of formula (-XIV) emi24.2 which is subjected to the action of a cleaving agent of the ester function carried by the acetylenic carbon, to obtain the compound of formula (Xv frames)

EMI24.3

which is subjected to the action of a hydrogenating agent provided to obtain the compound of formula (IX).In a preferred embodiment of the method of the invention above, - alk in formula (V-) represents a radical

terbutyle

, - the agent acid hydrolysis is paratoluene sulfonic acid; esterifying the compound - (XIII is) is carried out by reacting the compound (XIII is) with the alcohol (II), in the presence of dicyclohexyl carbodiimide or diisopropyl carbodiimide-; - cleavage of the ester (-XIV) is by using a metal powder, for example the zinc powder, in acid medium; - provided the hydrogenating agent is hydrogen in the presence of a catalyst such as palladium, in the presence of traces of quinoline.The above method comprises a variant evident in accordance which the stages hydrogenation and esterification are reversed.The invention thus also relates to a method as defined above, characterized in that a compound of formula (Xv frames)

EMI25.1

wherein A 'is as defined hereinbefore, to the action to' an esterifying agent, to obtain the compound of formula (X-) emi25.2 wherein R and a 'are defined as above, which is subjected to the action of a hydrogenating agent provided, to obtain the compound of formula (I-').Preferential conditions for carrying out the method above are identical to those that have been defined for the like operations

denirnent

experie.In the case where it is desired to prepare a compound of formula (I-') wherein R is an alkyl radical substituted with one or more hydroxy radicals, first prepared, according to any of the methods above, a compound of formula (I-') wherein R is an alkyl radical substituted with one or more hydroxy protected, for example by a group

dioxolanyl

or tetrahydropyranyl, and hydrolyzing said compound for thermally?a hydrolyzing agent acid.The hydrolyzing agent acid used in the above method can be, for example, hydrochloric acid or paratoluene sulfonic acid.Most of the methods just described above, lead to compounds in which the double bond at the geometry Z that are naturally the methods that are most suitable for the preparation of compounds of formula (I-') in which the double bond at the Z-geometry.Excellent yields are obtained as shown clearly the experimental part exposed hereinafter.The compounds (III), (IV) and (VIII), as well as the compounds (xt is) and (s), obtained during the implementation of the method of

ltinvention

are new chemical products.The invention therefore also relates to these products, to novel chemical products, and more particularly, as intermediate products for the preparation of compounds of formula (I-') as previously defined.Example 1: (cis-1r) 2.2-dimethyl 3 and (2) the 3 -/(2.2.2-a trifluoroethoxy) 3 oxo 1 a-propenyl/cyclopropane carboxylate of (e)- α-cyano 3-phenoxy benzoyl.Is mixed under agitation 1.3 g acid (cis-1r) 2.2-to-dimethyl 3/(Z-) 3-oxo-substituted 3 - (2.2.2-a trifluoroethoxy)/Pro -

penyl

-cyclopropanecarboxylic acid, pyridine and 0.1 cm3 15 cm3 of methylene chloride and then added 1.05 g of dicyclohexyl carbodiimide. Then added 1.35 g of (e) α-hydroxy 3-phenoxy benzene acetonitrile solution in 5 cm3 of methylene chloride. Stirred 5 hours at room temperature, filter the insoluble and flushes to methylene chloride. The filtrate is added 2n hydrochloric acid. Decanted, washed with water, dried and causes dry. The oil obtained is purified by chromatography on silica (eluent cyclohexane ethyl acetate 95 - 5). This provides 1.33 g of the desired product.- 420 * 20=+ (c=0.7 benzene) NMR cdcl3: 1.26 and 1.28 ppm of H-methyls in 2, 1.97 - 2.11 H of the cyclopropane carbon 1, 3.1 to 3.4 H of the cyclopropane carbon 3, to 6.9 to carbon H of the

propenyl

radical L, 5.9 - 5.93 H of the

propenyl

radical carbon 2, 6.3 H of the carbon bearing the NC, 4, -3 to 4.7 hr of the radical trifluoroethoxy.In the example 1 acid used is prepared as follows -: T-preparation: acid (cis-1r) 2.2-to-dimethyl 3/(Z-) from 3 - (2.2,

2trifluoroéthoxy

) 3 oxo-L-

propenyl

/-cyclopropanecarboxylic acid.Step a: (cis-1r) 2.2-dimethyl 3 - (3 hydroxy 3 oxo 1 a-

propynyl

) of 1.1 to-dimethylethyl-cyclopropane carboxylate.26 g of introduced (cis-1r) 2.2-to-dimethyl 3 - (2,

2dibromovinyl

) cyclopropane carboxylate of the L, L dimethylethyl in 175 cm3 of anhydrous tetrahydrofuran. Then added - 650c 60 cm3 solution 20% of butyl lithium in cyclohexane. I hour is agitated to - 60 C. and then bubbled through a carbon dioxide flow one and a half hours, the reaction mixture is poured into ice water with added soda n washed to ether. The alkaline aqueous phase is acidified to pH 4 and extracted with ether. The organic phases are dried, causes dry under reduced pressure. The obtained product is recrystallized in petroleum ether (60 - 800 c) .on to EB then obtains 8.3 g of the desired product melts at 1440 C..NMR

CDC13

-: 1.22 ppm based and 1.37: methyls protons 2 cyclopropane, 1.78: 1 and 3 proton in cyclopropane, L., 47: proton of the

terbutyle

, 8.25: proton-groupementemi28.1Step b: (cis-1r) 2.2-dimethyl 3 / - 3 oxo - (2.2.2-a trifluoroethoxy) 1 a-

propynyl

/cyclopropane carboxylate of 1.1-dimethyl ethyl.4 g of the introduced product prepared in step a, 3.5 g of

dicyclohexylcarbociimide

, in a solution of methylene chloride and 20 cm3 1 cm3 pyridine. Is maintained under stirring the reaction mixture for one hour.Then added 2.15 g of 5 cm3

trifluorcéthanol

and methylene chloride. Is maintained under stirring at 20 C. for 16 hours. Is filtered, and rinses to methylene chloride. Bringing the filtrate to dry. Is taken up with ether sulfuric, hydrochloric acid n-washed and then water and dry.Is concentrated and isolates 5 g of a product that

lton

silica chromatography (eluent-benzene-ethyl acetate (95 - 5). The result is 3.5 g of desired product.NMR cdcl3: 1.2 ppm. h of 1.37 and methyl in 2, 1.77 H of carbons 1 and 3 cyclopropane, 1.43 h of 1.1 to-dimethylethyl methyl radical, 4.3 to 4.7 hr of the radical trifluoroethoxy.Step c: acid (cis-LR1)/2.2-dimethyl 3 to 3 oxo-3 - (2.2.2 tri - fluoroethoxy and 1 a-

propynyl

/-cyclopropanecarboxylic acid.Refluxes is a mixture containing 3.3 g of the product prepared in the previous step, 100 mg of toluene and 30 cm3 paratoluene sulfonic diacid. Refluxing is maintained until the end of the off-gas. Is cooled, washed with water, dried and causes dry. This provides 2.6 g of the desired product is used as such in the following step.Step d: acid (cis-1r) 2.2-dimethyl (2)/3 and - 3 oxo-3 - (2.2,

2trifluoroéthoxy

) cyclopropanecarboxylic acid/1 a-propenyl.Is placed in a flask connected to an apparatus to hydrogen

dthydroxyde

500 mg 10% palladium on barium sulfate, 5 cm3 and ethyl acetate. 2 g of the added product prepared in the previous step, 45 cm3 of ethyl acetate and 0.5 cm3 quinoline. Is hydrogen until the end of the uptake. Is filtered. The filtrate is washed with n hydrochloric acid and then water, and causes it to dry. 2 g of an obtained product which chromatography on silica (eluent hexane, ethyl acetate, acetic acid (70 - 30 - 1) this gives 1.3 g of the desired product.NMR spectrum cdc13 SPMs 1.3 and 1.32 hr methyls in 2, 1.92 - 2.06 H of the carbon 1 cyclopropane, 3.07 to 3.38 H of the cyclopropane carbon 3, 6.6 to 6.9 H of the propenyl radical 1 carbon, 5.9 - 6.0 H of the carbon 2 of the radical propenyl, 4.3 to 4.7 hr of the radical trifluoroethoxy.Example 2: (cis-LR1) 2.2-to-

dlméthyl

-a 3 - / - (Z-) 3 oxo-3 - (2.2.2 - trifluoroethoxy) 1 a-propenyl/cyclopropane carboxylate of (1s) 2-dimethyl 4 oxo-3 - (2 a-propenyl) 2 a-Cyclopent-to-1-yl.1.9 g of mixed acid (cis-1r) 2.2-to-dimethyl 3/(Z-) 3 oxo-3 - (2.2.2-a trifluoroethoxy) cyclopropanecarboxylic acid/1 a-propenyl, 12 cm3 of methylene chloride and 100 mg of dimethylamino pyridine. 1.4 g of is then introduced dicyclohexyl carbodiimide, followed by 1.1 g of (e) from 3 - (2 a-propenyl) 1 hydroxyl 2-methyl 4 oxo and cyclopent-to-2-ene and 5 cm3 of methylene chloride. Is maintained under stirring at room temperature for 2 hours. Removed by filtration the insoluble formed. The filtrate is washed with 0.5 n-hydrochloric acid, then with water, dried, and causes it to dry. This results in 3 g of a product wherein the product is chromatographed on silica (eluent benzene-acetate (95 - 5) methyl).This gives 2.2 g of the desired product.+ +=380 + 2.50 (c=0.5% benzene) NMR spectrum cdcl3 1.29 ppm. and 1.32 h of 2 methyl-cyclopropane, 1.97 - 2.11 R 1 cyclopropane, 3.05 to 3.37 H 3 cyclopropane, 6.7 to 7 H of the carbon 1 of the radical propenyl, 5.9 6, 1emi30.1 R of the propenyl radical having 2 carbon, 4.3 to 4.75 hours of the radical trifluoroethoxy, 5.7 H of the cyclopentene to α of the c02 2 H of the methyl carried by the cyclopentene, 4.8 to 5.25 H 3 of the propenyl carried by cyclo pentene.Example 3: (IR-cis-) 2.2-to-dimethyl 3/(Z-) 3 oxo - 3 - (phénylmétho - xy) 1 a-propenyl/cyclopropane carboxylate of (1s)

αcyano

and 3 a-Phe -

noxy

benzyl.Step a: chloride acid (cis-1r) 2.2-to-dimethyl 3 - (Z-)/3 oxo-3 - (Phenylmethoxy) cyclopropanecarboxylic acid/1 a-propenyl.Stirred 5 hours under nitrogen stream, a mixture containing 1.6 g acid (cis-1r) 2.2-to-dimethyl 3/(Z-) 3 3 oxo (phenylmethoxy) 1 a-

propenylicycloprcpane

carboxylic, 10 cm3 isoprene and 1 cm3 of thionyl chloride, concentrate and thus obtains 2 g of a product is used as such in the following step.Step b: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (Phenylmethoxy) 1 a-propenyl/(1s) cyclopropane carboxylate of α-cyano 3-phenoxy benzyl.1 g of the introduced product prepared in step a in a solution containing 700 mg of (e) alpha-hydroxy 3-phenoxy benzene acetonitrile, 20 cm3 0.6 cm3 of benzene and pyridine. The reaction mixture is maintained under stirring for 16 hours, at room temperature, poured over an ice-water mixture and hydrochloric acid n the suspension obtained is agitated and extract to benzene. Benzene extracts are washed, water, dry, filter and causes dry. 1.5 g of an obtained product which chromatography on silica (eluent cyclohexane ethyl acetate (8 - 2)).This provides 861 mg of the desired product melting 830c.@==690 + 50 + (c=0.2% benzene) d-NMR spectrum cdcl3 1.25 ppm to 2 methyls in H-cyclopropane, 6.33 H of the carbon bearing the NC.Preparing the II: acid (cis-1r) 2.2-dimethyl 3 - (Z-)/3 oxo-3 - (phenyl) - cyclopropanecarboxylic acid/1 a-propenyl.Step a: (cis-1r) 2.2-to-dimethyl 3/(Z-) 2 carboxy ethenyl/cyclopropane carboxylate of 1.1 to-dimethylethyl.Hydrogen is 2 g of (cis-1r) 2.2-dimethyl .3/2 carboxy/ethynyl cyclopropane carboxylate of 1.1 to-dimethylethyl 40 cm3 in ethyl acetate in the presence of 0.38 g of 10% palladium hydroxide on barium sulfate and 0.4 cm3 quinoline. Is filtered, washing the filtrate to 0.5 n-hydrochloric acid, then with water until neutrality, dried, concentrated to dry under reduced pressure and 2 g of the product obtained melts at 94 C. lookout shee.Step b: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo-3 - (phenyl) - 1 a-propenyl/cyclopropane carboxylate of 1.1 to-dimethylethyl.2.4 g of the introduced product prepared in step a in 20 cm3 of ethyl acetate. Then added 2.34 g of 0-benzyl-n-, n

dìisopropyl

isourea (described by

ESCHIMDT

and neck

Liebig

ANNs.In. 1965, 685 161.). Is stirred 16 hours at the temperature the AM -

biante

, filter and concentrate the filtrate under reduced pressure.Obtained 4.3 g of a yellow oil that chromatography on silica (eluent benzene cyclohexane (7 - 3)). This provides 2 g of the desired product.NMR spectrum cdcl3 1.22 ppm of 1.28 and h of 2 methyl-cyclopropane, 1.77 - 1.91 H of the carbon 1 cyclopropane, 2.98 to 3.3 H of the cyclopropane carbon 3, and 6, and 5 - to 6.8 H of the carbon 1 of the radical propenyl, 5.8 - 6 H of the carbon 2 of the radical propenyl, 1.43 h of dimethylethyl methyl radical, a methoxy radical 5.1 H of the Phenylmethoxy.Step c: acid (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo-3 - (phenyl) cyclopropanecarboxylic acid/1 a-propenyl.Is heated to 90 c is a mixture containing 2 g of the product prepared in the previous step, 30 cm3 toluene, 100 mg of paratoluene sulfonic acid. Is maintained under stirring for 2 hours. The mixture is brought to dry and obtains 2 g of a product wherein the product is chromatographed on silica (eluent: Cyclohexaneacetate 60/40/1

d'éthyle

-acetic acid).This gives 1.4 g of the desired product.NMR spectrum cdcl3 1.25 ppm to 1.3 and 2 h of methyl-cyclopropane, 1.84 - 1.98 H of the carbon 1 cyclopropane, 3.14 to 3.43 H-R of the cyclopropane carbon 3, 6.4 to 6.77 R of the carbon 1 of the radical propenyl, 5.98 H of the carbon 2 of the radical propenyl.Example 4: (cis-1r) 2.2-to-dimethyl 3 - (Z-)/3 oxo-3 - (methoxy - phenyl) - 1 a-propenyl/cyclopropane carboxylate of (1s) -

2méthyl

-to-4 oxo-3 (2 a-propenyl) 2 a-Cyclopent-to-1-yl.1 introduced g chloride acid (cis-1r) 2, 2diméthyl/3. (a Z) 3 oxo-3 (

phényulméthoxy

)/1 a-

propenyl

-cyclopropanecarboxylic acid in a mixture of 450 mg of (e) (2 a-

propenyl

) 3 1 hydroxy 2-methyl 4 oxo and cyclopent-a 2 in-1-yl, 20 cm3 0.6 cm3 of benzene and pyridine. Is maintained under agitation for 16 hours and contributes the reaction mixture on an ice-water mixture and extracted n hydrochloric acid to benzene, benzene phases combined, washed with water, dried and causes dry. 1.5 g of an obtained product that 1' is chromatography on silica (eluant: cyclohexane-ethyl acetate (8 - 2)).This provides 500 mg of the desired product.==+ 37 + 2.5 (c=0.5% benzene) and 1.27 ppm in spectrum

RNN

cdcl3 1.31 h of 2 methyl-cyclopropane, 1 carbon as HDu 1.87 - 2 cyclopropane, I-3.12 to 3.45 as HDu cyclopropane carbon 3, 5.8 to 6.8 H 1 and 2 of the radical

propenyl

, 5.2 H of the methoxy radical phenyl, 5.6 to 5.7 R of the cyclopentene to the co2 2 H of the methyl carried by the cyclopentene, to to 5.2 H of the propenyl carried by the cyclopentene.Example 5: (cis-1r) 2.2-dimethyl 3/(Z-) - 3 oxo-3-phenoxy-

1propényl

/

carbxoylate

(e) cyclopropane derivatives of α-cyano 3-phenoxy benzyl.By operating as to the example 1, 1.5 g of from

aclde

(cis-1r) 2.2-dimethyl 3/(Z-) 3 oxo-3-phenoxy-1propenyl/1.45 g of cyclopropane carboxylic and (e)- α-hydroxy 3-phenoxy benzene acetonitrile, 1.8 g of the product obtained desired.d-α==54 + 2.5 + (c=0.5% in benzene) NMR spectrum

CDCl

1.25 ppm to 2 H cyclopropane, 1.97 - 2.12 R 1 cyclopropane, 3.25 to 3.6 R 3 cyclopropane, 6.6 to 7 H 1 of the radical propenyl, 6.1 - 6.3 H 2 of the radical propenyl.6.9 to 7.7 hr aromatic radical 3-phenoxy phenyl.Preparation lll @ acid (cis-1r) 2.2-dimethyl 3/(Z-) 3 oxo 3-phenoxy-1 a-propenyl /-cyclopropanecarboxylic acid.Step a: (cis-1r) 2.2-dimethyl 3 / - 3 oxo-3-phenoxy-1 a-

propynylcyclopropnae

carboxylate/1.1 to-dimethylethyl.25 g of dissolved (cis-1r) 2.2-to-dimethyl 3 - (2 ', 2' -

dibromovinyl

) cyclopropane carboxylate of 1, 1-dimethyl ethyl in 250 cc of tetrahydrofuran. Then insert -65 C. with stirring, to a solution of 48 cm3 20 > of butyllithium in cyclohexane. The stirring is maintained for one hour to - 650c and introduced 9.6 cm3 of phenyl chloroformate. Again is maintained under stirring at - 650c, for one hour, and allowed to return to room temperature while maintaining the stirring. is poured onto a saturated aqueous solution of phosphate

monosodiaue

, extracted with ether, washed with water, dried and obtains 24.6 g of an oil which is purified by chromatography on silica (eluant: cyclohexane-ethyl acetate (9 - 1)). Thus isolated 14.4 g of the desired product.NMR spectrum CDCs 13 PDM-1.23 and 1.42 hr methyls in 2 cyclopropane, 1 H 3 and 1.82 cyclopropane, 1.5 hr of the radical dimethyl ethyl, 7 to 7.6 hr aromatic.Step b: (cis-1r) 2.2-dimethyl 3 - (Z-)/3 oxo-3-phenoxy-

1propényl

/cyclopropane carboxylate of 1.1-dimethyl ethyl.In the presence of 800 mg of palladium hydroxide on barium sulfate, 0.8 cm3 quinoline and 20 cm3 of ethyl acetate, hydrogen is 4 g of the product prepared in step a in solution in 60 cm3 of ethyl acetate, filtered and adds 200 cm3 solution 2n hydrochloric diacid. Decanted, washed with water and dried. Obtained 4.1 g of an oil which is purified over silica (eluant: cyclohexane-ethyl acetate (95 - 5)). 3.35 g of the product obtained desired.NMR spectrum ' cdcl3 ppm of 1.23 and 1.3 R 2 cyclopropane, 1.83 - 1.97 R 1 cyclopropane, 3 to 3.33 H 3 cyclopropane, methylethyl group H of the 1.44, 6.7 to 7 H 1 propenyl radical, 6.03 - 6.21 H 2 of the radical propenyl, 7 to 7.5 R-aromatic.Step c: acid (cis-1r) 2.2-dimethyl 3 - (Z-)/3 oxo 3-phenoxy carboxylic

cyclopropnae

/1 a-propenyl.It carries a refluxing a mixture of 3.3 g of the product prepared in the previous step, 100 mg of 35 cm3 of toluene and paratoluene sulfonic acid monohydrate. The backflow is stopped immediately after the end of the off-gas. The mixture is brought to dry under reduced pressure and obtains 3.4 g of a product wherein the product is chromatographed on silica (eluant: cyclohexane acetate

d'éthyle

-acetic acid (70 - 30 - 1). 2.4 g of the product obtained melts at 57 C. sought.NMR spectrum cdcl3 1.25 ppm of 1.33 to 2 methyls in H-cyclopropane, 1.9 - 2.04 cyclopropane 1 H, 3 H 3.2 to 3.5 cyclopropane, 6.6 to 6.9 H 1 of the propenyl, 2 of the propenyl R into 6.0 - 6.2.Example 6: (cis-1r) 2.2-dimethyl 3/(Z-) - 3 oxo-3-phenoxy-1 - propenyl/cyclopropane carboxylate of (1s) 2-methyl 4 oxo-3 (2 a-

propenyl

) 2 a-Cyclopent-to-1-yl.By operating as to the example 2, from 1.5 g acid (cis-

îR

) 2.2-dimethyl 3/(Z-) - 3 oxo 3-phenoxy-1 a-propenyl-cyclopropanecarboxylic acid and 1/(O) g of 3 - (2 Pro-

penyl

) I-hydroxy 2-methyl 4 oxo and cyclopent-a 2 in-1-yl, 1.6 g of the product obtained desired.d-α=2.5 + 66# (c=0.5% benzene) NMR spectrum cdcl3 1.26 1.33 ppm to 2 H and cyclopropane, 1.95 - 2.09 H 1 cyclopropane, 5.7 H of the cyclopentene to α C02, 4.8 to 5.2 H 3 of the propenyl carried by cyclo pentene, 2 R of the methyl carried by the cyclopentene, 6.1 to 6.7 H of the propenyl carried by cyclopropane, 7 to 7.7 hr aromatic.Example 7: (cis-1r) 2.2-dimethyl 3/(Z-) - 3 oxo-3-methoxy methoxy 1 a-propenyl/cyclopropane carboxylate of (R) α-cyano-benzyl 3-phenoxy.Step a: (cis-1r) 2.2-dimethyl 3 - (3 oxo-3-methoxy methoxy

propynyl

1) cyclopropane carboxylate of (R) α-cyano-benzyl 3-phenoxy.Is cooled to + 100c 3 g of a solution of (cis-1r) 2.2-dimethyl 3 - (3 hydroxy 3 oxo 1 a-

propynyl

) cyclopropane carboxylate of (R) α-cyano-benzyl 3-phenoxy in anhydrous dimethylformamide 30 cm3, adds per fraction, 300 mg of sodium hydride to 61% in oil and then 15 min, 2.5 cm3 SO -

lution

ether

chlorométhyliaue

prepared as below. The mixture is stirred 2 hours, poured onto an aqueous solution of monosodium phosphate and extract with ethyl acetate, washed with water and concentrated to dry clothes. The residue is chromatography on if running, it with a mixture: cyclohexane-ethyl acetate (75/25) and 2 g of expected product is collected.NMR cdcl3 ppm of 1.23 - 1.27 and 1.35 - 1.45 methyls protons 2 cyclopropane, 1 and 3 1.95 proton in cyclopropane, 5.28 proton-methylene methoxy methoxyl, 3.5 methyl proton from methoxy methoxyl, 6.42 and 6.47 proton abstraction carried by the same carbon than CN, 6.92 to 7.58 aromatic protons.Preparation of the ether solution

chlorométhvliaue

.4.5 cm3 mixed methylal and 0.52 cm3 methanol and then slowly added 3.53 cm3 of acetyl chloride. The mixture is stirred for 36 hours at room temperature to obtain the expected solution.Step b: (cis-1r) 2.2-dimethyl 3/(Z-) - 3 oxo-3-methoxy methoxy 1 a-propenyl/cyclopropane carboxylate of (R)- α-cyano 3-phenoxy benzyl.2.2 g of product hydrogen is obtained as above in 50 cm3 of ethyl acetate in the presence of 450 mg of 10% palladium hydroxide on barium sulfate in 30 cm3 of

cétate

0.5 cm3 and ethyl-quinoline. Is filtered, washing the filtrate to n-hydrochloric acid, water, dry and causes dry. The residue on silica is chromatography, eluted by a mixture: cyclohexane-ethyl acetate - (8 - 2) and 1.2 g of expected product is collected.#3=+ 41 (c=0.3% chcl3) NMR CDCs 13 ppm 1.27 - 1.28 and 1.33 - 1.35 methyls protons 2 cyclopropane, 1 proton at 1.93 - 2.1 cyclopropane, 3.17 to 3.5 proton at 3 cyclopropane, 6.47 to 6.1 . 82 that the proton-ethylenically unsaturated, 5.85 - 6.0 5.88 - 6.1 and proton from ethylenic in 2, 5.27 ch2 5.3 and proton-methoxy, 3.47 and 3.5 methyl protons of the methoxy, 6.4 carried by the same carbon than CN, 6.92 to 7.67 aromatic protons.The (cis-1r)/2.2-to-dimethyl 3 - 3 hydroxy - 3 oxo 1 a-

propynyi

/cyclopropane carboxylate of (R)- α-cyano 3-phenoxy benzyl used at the beginning of the example can be prepared in a manner analogous to that of the ester (e) later described, using the corresponding alcohol (R).Example 8 (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo 3-cyano-methoxy 1 a-

Drooényl

/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.Step a: (cis-1r) 2.2-dimethyl 3 / - 3 oxo 3-cyano-methoxy

propynyl

1/cyclopropane carboxylate of (R)- α-cyano 3-phenoxy benzyl.Operation is carried out as in example 7 using 2 cm3 of chloroacetonitrile; after extraction with ether and elution with a mixture: cyclohexane-ethyl acetate (9 - 1), 2.69 g of product is obtained expected.Step b: cis-t1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo 3-cyano-methoxy 1 a-propenyl/cyclopropane carboxylate of (R) α-cyano-benzyl 3-phenoxy.By operating as to the example 7 starting at 2.69 g of the product obtained previously, 2.02 g of product is obtained expected following elution with a mixture: cyclohexane-ethyl acetate (9 - 1).Step c: cis-

çîr

) 1 a-propenyl/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.Silica chromatography is 1.4 g of the above product, elutes at methylene chloride and 0.41 g of expected product is obtained.d-α==550 + 1.5 + (c=1% chcl3) example 9: (' IR-cis-) 2.2-dimethyl 3 - (Z-)/3 oxo - 3 a-ethoxyethoxy 1 a-propenyl/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.Step a: (cis-1r) 2.2-dimethyl 3 / - 3 oxo-3 a-ethoxyethoxy 1 a-

propynyl

/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.Is cooled to O - + 50C fabrics, 2 g of (cis-1r) 2.2-to-dimethyl 3/3 hydroxy - 3 oxo 1 a-

propynyl

) cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy, 20 cm3 - methylene chloride and 0.7 cm3 of ethoxy ethanol. Added 1.1 g-of -

dicyclohexylcarbodiimide

, 5 cm3 of methylene chloride and 15 mg of dimethyl aminopyridine. 1 hour to + 50c is agitated and 2 hours at room temperature. Is filtered, and the filtrate concentrated to dry the residue on

sillce

chromatography, eluted by a mixture: cyclohexane-ethyl acetate (75 - 25) and 1.3 g of expected product is obtained.NMR cdcl3 1.22 - 1.32 ppm to 2 methyls protons cyclopropane, 1 and 3 in proton 1.93 cyclopropane, 4.17 to 4.38 proton in 1 COO-ch2-to-ch2-to-0 3.55 to 3.73 proton in 2 COO-ch2-to-ch2 6.57 - O-proton abstraction carried by the same carbon than CN 7 to 7.67 aromatic protons 1.08 - 1.2 - 1.3 and 1, 52 (O-) protons of

éthyleStade

b.: (cis-1r) 2.2-to-dimethyl 3/(Z-) - 3 oxo substituted 3 - (ethoxy - phenazinetho XY-) 1 a-propenyl/cyclopropane carboxylate of phenoxy benzyl.By operating as to the example 7, step b, from 1.3 g of the product obtained above is obtained 1.0 g of desired product.+=37, 5 2.5 (c=0.5% chcl3) #10 g.: (cis-LR1) 2.2-dimethyl 3 - (Z-)/- 3 oxo (R) 3 (1 and 1 a-

1trifluorométhyl

ethoxy) 1 a-propenyl cyclopropane carboxylate of (e)- α-cyano 3-phenoxy benzyl.Operation is carried out as in step b of example 7 in 2.6 g of usable are heterozygous (cis-1r) 2.2-to-dimethyl 3 / - 3 oxo - 3 and ((R) 1.1.1 tri fluoromethyl ethoxy)

propynyl

/cyclopropane carboxylate of (e) α-cyano-benzyl 3 para. After elution from a mixture cyclohexane ethyl acetate (9 - 1) is obtained 2.1 g of desired product.440 + 2 + +=(c=0.4% benzene) preparation of (cis-- 1r) 2.2-to-dimethyl 3 - 3 to 3 oxo/((R) 1.1.1 tri

fluorométhyléthoxy

)

propynyl

/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.Operation is carried out as in step a of 1' example 9 using 4.6 g of ethanol and 1.1.1-trifluoromethyl 3.8 g of (cis-1r) 2.2-dimethyl 3 and 13 oxo 3 hydroxy-

propynyl

/cyclopropane carboxylate of (e)- α-cyano 3-phenoxy benzyl to obtain, after elution from a mixture cyclohexane ethyl acetate (8 - 2) 2.6 g of desired product.Example it: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2 difluoro - ethoxy) propenyl/

cylcopropane

(e) carboxylate-cyano 3-phenoxy benzyl.Step a: (cis-1r) 2.2-dimethyl 3 / - 3 oxo - 3. (2.2 to-

difluoroéthoxy

)

propynyl

/cyclopropane carboxylate of

terbutyle

.By operating as in step a of example 9 from 5 g of (cis-1r) 2.2-dimethyl 3/3 hydroxy - 3 oxo-1 a-

propynyl

/cyclopropane carboxylate of

terbutyle

and after elution from a mixture n-hexane-ether (7 - 3) is obtained isopropyl 5.25 g of desired product.The IR chcl3

conj

2232 cms and 1 C. 1725 cm==from 0 ester of asymmetric 1710 cm. and

1EMI38.1

<tb> gEMs <SEP> dimethyl <SEP> (1393 <SEP> cms L<tb> <SEP> 1380 <SEP> cms L <SEP> <tb>

terbutyle

1372 cms-to-1stade b.: acid (cis-1r) 2.2-dimethyl 3 / - 3 oxo - 3. (2.2 to-

difluoroéthoxy

) 1 a-

propynyl

/

carboxylane

cyclopropane group.Heated at reflux 5.2 g of the product obtained above, 500 mg of paratoluene sulfonic acid in toluene during 25 minutes to 40 cm3. After cooling added 400 cm3 ether, washed with water, drying the organic phase and concentrate to dry to obtain 4.1 g of desired product.Step c: (cis-1r) 2.2-dimethyl 3 / - 3 oxo - 3. (2.2 to-

difluoroéthoxy

) 1 a-

propynyl

/cyclopropane carboxylate of (e)- α-cyano 3-phenoxy benzyl.By operating as in step a of example 9 from 4.1 g of the acid obtained above and 4.5 g of (e)- α-cyano 3-phenoxy benzyl obtained, after elution from a mixture petroleum ether (40 - 700 c to EB) - isopropyl ether (6 - 4) 4.7 g of desired product.

EMI39.1

<tb>AN IR <SEP> Chcl3. <SEP> <tb>THE OH <SEP> 3580 <SEP> cms-a 1 <SEP> gEMs <SEP> the di <SEP> The Mth <SEP> 1392 <SEP> cms L<tb> <SEP> 1380 <SEP> cms-a 1<tb>

conj

<SEP>

conj

<SEP> 2235 <SEP> cms-a 1<tb> <SEP> THE O==C. <SEP> the ester <SEP> 1755 <SEP> cms-a 1<tb> <SEP> the ester <SEP>

conj

<SEP> 1725 <SEP> cms-a 1<tb> <SEP> aromatic <SEP> 1588 <SEP> cms-a 1<tb> <SEP> 1488 <SEP> cms-a 1<tb> Step d: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2 difluoro ethoxy) propenyl/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.Hydrogen is 4.7 g of the product obtained above - of-the same manner as in step b of example 7. after elution from a mixture n-hexane-ether (7 - 3) -

isopropyllque

obtained 3.2 g of desired product.==440 + 2.5 + (c=0.5% chcl3)

DExemple

12: (cis-1r) 22-dimethyl 3 - / - (Z-) 3nxo and 3 - (2.2-dichloro-- ethoxy) 1 a-propenyl/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.Stdcdbpg0123stade has: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo-3 - (2.2 to-

dichloroéthoxy

) 1 a-propenyl/cyclopropane carboxylate of

terbutyle

.Operation is carried out as to the example 9 step a from 4.8 g of (cis-1r) 2.2-dimethyl 3 - (Z-)/3 hydroxy 3 oxo 1 a-propenyl/cyclopropane carboxylate of

terbutyle

and 2 cm3 of 2, 2dichloroéthanol. After elution from a mixture cyclohexane ethyl acetate (9 - 1) is obtained 5.6 g of desired product.Step b: acid (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo-3 - (2.2-dichloro-ethoxy) cyclopropanecarboxylic acid/1 a-propenyl.Operation is carried out as in step b of example 11 starting from 5.6 g of the above product and obtains 4.5 g of desired product.Step c: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo-3 - (2.2-dichloro-ethoxy) 1 a-propenyl/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.Operation is carried out as in step a of example 9 from 3 g of the product obtained in b and 2.25 g of alcohol (e) α-cyano - 3-phenoxy benzyl. After elution by mixtures cyclohexane ethyl acetate (8 - 3) and (9 - 1) is obtained 1.6 g of desired product.540 + 20 +=D. (c=1% in benzene) the following examples are prepared analogously to that described in step a of example 9 from 1) acid (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2 to-

difluoroéthoxy

) 1 a-propenyl/cyclopropanecarboxylic acid and the corresponding alcohol.Example 13: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2 to-

difluoroéthoxy

) 1 a-propenyl/cyclopropane carboxylate of (R) α-cyano-methyl 2 a-pyridyI

6phénoxy

.d-α=+ 50.5# 2 (c=0.8% chcl3) 14 g.: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2 to-

difluoroéthoxy

) 1 a-propenyl/cyclopropane carboxylate of α-cyano - (R-) 3-phenoxy benzyl.d-α=+ 117, 5# 3 (c=0.6% chcl3)

Exemjple

15: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2 to-

difluoroéthoxy

) 1 a-propenyl/cyclopropane carboxylate of/3 propargyl - 2.5 a-

dioxpimidazolidinyl

/methyl.Hoc (c=1% chcl3) + 180 + 20=16 g.: (cis-1r) 2.2-dimethyl 3 - / - (Z-) - 3 a-axoglial 3. (2.2 difluoro - ethoxy) 1 a-propenyl/

cyclotrotane

carboxylate (R.) α - ethynyl 3-phenoxy benzyl.td=+ 47 + 1.5 (c=1% chcl3) acid (cis-

îR

) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2,

2difluoro

ethoxy) 1 a-propenyl/cyclopropanecarboxylic acid was prepared in a manner analogous to that described in the preparation-VI from 2.2 to-difluoroethanol.20) acid (cis-1r) 2.2-to-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2 fluoro ethoxy) 1 a-propenyl/cyclopropanecarboxylic acid and the corresponding alcohol.Example 17: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2 fluoro ethoxy) 1 a-

propénylî

cyclopropane carboxylate of (3 propargyl 2.5 a-

dioxoimidazolidinyl

) methyl.d-α=18 + #2 (c=1% chcl3) 18 g.: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2 a-fluoroethoxy) - 1 a-propenyl/cyclopropane carboxylate of (R) α-cyano-(6-phenoxy 2 a-pyridyI) methyl.d-α=+ 49.5# 2, 5 (c=0.5% chcl3) example 19: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2-fluoro-ethoxy) - 1 a-propenyl/cyclopropane carboxylate of (the R) α-methyl 3-phenoxy 3-phenoxy benzyl benzoyl. benzyl. -: 123 + 1.5 +=(c=1% chcl3) example 20': (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2 fluoro - ethoxy) - 1 a-propenyl / α-ethynyl-cyclopropane carboxylate 3-phenoxy benzyl.470 + 1.5 +==(=from 1% chcl3 - C.) acid (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3. (2fluoro ethoxy) 1 a-propenyl/cyclopropanecarboxylic acid was prepared in a manner analogous to that described in the preparation-VI from the 2 fluoro ethanol.30) acid (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (or 2 - (1.1.1, 3.3.3-to-hexafluoropropylene) propoxyl)/1 a-propenyl-cyclopropanecarboxylic acid (preparation-VI) and the corresponding alcohol.Example 21: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (or 2 - (1.1.1, 3.3.3-to-hexafluoropropylene) propoxyl) 1 a-propenyl/cyclopropane carboxylate of α - (R-) ethynyl 3 a-

nhénoxy

benzyl.d-α==+ 31.50 + 1.50 (c=1% chcl3) 22 g.: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (or 2 - (1.1.1, 3.3.3-to-hexafluoropropylene) propoxyl) 1 a-propenyl/of the cyclopropane

caboxylate

(R.)' α - methyl 3-phenoxy benzyl.The d=+ 97# 2 (c=1% chcl3) example 23 (IR-cis-) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (or 2 - (1.1.1, 3.3.3-to-hexafluoropropylene) propoxyl) 1 a-propenyl/cyclopropane carboxylate of (e)- α-cyano 3-phenoxy benzyl.With d=(c=0.5% benzene) 23.50 + 20 + 24 g.: (cis-1r) 2.2 '-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (or 2 - (1.1.1, 3.3.3-to-hexafluoropropylene) propoxyl) 1 a-propenyl/cyclopropane carboxylate of 5.6 3.4

,,

-to-tetrahydrophthalimido methyl.d-α=- 30# 1 (c=1% chcl3) 25 g.: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (or 2 - (1.1.1 3.3.3-to-hexafluoropropylene) propoxyl) 1 a-propenyl/cyclopropane carboxylate of (R) a cyano 6-phenoxy 2 and the pyridyl-methyl.d-α + 2.5=33.5 (c=0.2% chcl3) #4) acid (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2,

2trifluoro

ethoxy) 1 a-propenyl /-cyclopropanecarboxylic acid (preparation of I) and alcohol, corresponding.Example 26: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2,

2trifluoro

ethoxy) '1 a-propenyl/cyclopropane carboxylate of (3 propargyl -2, 5' a-

dioxoimi'dazolidinyl

) methyl.α=- - 40 + 10 (c=1% benzene) 27 g.: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2,

2trifluoro

ethoxy) 1 a-propenyl/cyclopropane carboxylate of (the R) α-methyl 3-phenoxy

bezyle

.@ @ @ the d=+ 2 * (c=1% chcl3) example 28: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2,

2trifluoro

ethoxy) 1 a-propenyl/

carbxoylate

3.4.5.6-to-tetrahydrophthalimido or cyclopropane-methyl.d-α=2.5 + #2 (c=0.5% chcl3) example 29: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2,

2trifluoro

ethoxy) 1 a-propenyl/cyclopropane carboxylate of α - (R-) ethynyl 3-phenoxy benzyl.With d=, - 420 + 1.5 + (=1% chcl3. C.) 30 g.: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2,

2trifluoro

ethoxy) 1 a-propenyl/

carbxoylate

(R) of the cyclopropane-cyano 6-phenoxy 2 and the pyridyl-methyl.α-d +=46.5# 2 (c=0.7% chcl3) 5) of (cis-1r) 2.2-dimethyl 3 - (Z-)/3-hydroxy 3 oxo 1 a-propenyl/cyclopropane carboxylate of (e)- α-cyano 3-phenoxy benzyl (preparation VIII) and the alcohol

correspondantExemple

31: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2 4N-trichloro ethoxy) 1 a-propenyl/cyclopropane carboxylate of (e) α-cyano-benzyl

3phénoxy

.The d=+ 42, 5# 2 (c=0.5% benzene) example 32: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2 chloro-ethoxy) 1 a-propenyl/cyclopropane carboxylate of α-cyano - (O)- phenoxy benzyl substituted 3.d-α==390 + 4 + (c=0.25% benzene) example 33: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2-methoxy ethoxy) 1 a-propenyl/cyclopropane carboxylate of (e one cyano - benzyl

3phénoxy

.With d=37 5 + 2 + (c=1% chcl3) 34 g.: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - 1 (R) cyano-ethoxy) 1 a-propenyl/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.α-d +=64.5# 3 (c=0.3% chcl3) 35 g.: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2 fluoro ethoxy) 1 a-propenyl/

carbxoylate

(e) of the cyclopropane-cyano 3-phenoxy benzyl.=+ - 480 (c=0.25% benzene) example 36: ' (cis-1r) 2.2-dimethyl 3 - (Z-)/3 oxo - 3 a-

phénéthoxy

1 a-propenyl/

carbxoylate

(e) cyclopropane derivatives of α-cyano - 3-phenoxy benzyl.d-α=#2, 5 + 46 (c=0.5% benzene) example 37: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2.2-dimethyl

dioxolanyl

substituted 4 - (R)- methoxy) 1 a-propenyl/(e) cyclopropanecarboxylic

carbxoylate

of α-cyano - 3-phenoxy benzyl.the d=+ α=460' + 2 (c=0.75% benzene) 60) of (cis-

îR

) 2.2-dimethyl 3 - (Z-)/3 hydroxy - 3 oxo 1 a-propenyl/cyclopropane carboxylate of (R) α-cyano-benzyl 3-phenoxy and the corresponding alcohol.Example 38: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2-dimethyl amino ethoxy) 1 a-propenyl/(R) of the cyclopropane

carbxoylate

α-cyano - 3-phenoxy benzyl.d-α=+ 230 * 3 (c=0.25% chcl3) the (1r, cis-) 2.2-dimethyl 3 - (Z-)/3 hydroxy - 3 oxo

1propényl

/(SRV) cyclopropane carboxylate of the O (a cyano - 3-phenoxy benzyl used at the beginning of the example above was prepared in a manner similar to that of the ester (e)- α-cyano - 3-phenoxy benzyl of-formulations IV and VII.7) the (cis-1r) 2.2-dimethyl 3 - (Z-)/3 hydroxy - 3 oxo 1 a-propenyl/cyclopropane carboxylate of the c (R.) (- methyl 3-phenoxy benzyl (VIII-preparation) and the corresponding alcohol.Example 39: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2-methoxy ethoxy) 1 a-

propén'yl

/cyclopropane carboxylate of (the R) α-methyl 3-phenoxy benzylidene ' the.NMR cdcl3 1.22 - 1.25 ppm to 2 methyls protons 1.45 - 1.55 cyclopropane methyl protons of the ester in 1 cy

clopropane

5.7 'to 6.0' proton-proton of the methoxyl benzyl 3.42 4.22 to 4.38 proton in 1 of the ester in 3 of the breaded

cyclopro

3.55 to 3.72 proton in 2 of the ester in 3 of the breaded

cyclopro

5.85 - 6.05 and 6.32 to 6.8 40

éthyléniquesExemple

proton: (1r IC 'if) 2.2-to-

'diméthyl

-a 3 - / - (Z-) 3-oxo-substituted 3 - (1-methoxy ethoxy 1-trifluoromethyl) 1 a-propenyl/

carbxoylate

(e) of the cyclopropane-cyano 3-phenoxy benzyl.Was stirred under inert atmosphere 1.02 g of cis-

CîR

) 2.2-dimethyl 3 - (Z-)/- 3 oxo 3-chloro-1 a-propenyl) cyclopropane carboxylate of a cyano-OC(O)- 3-phenoxy benzyl and 9 cm3 of methylene chloride. 1.12 g of added 1-methyl 1-trifluoromethyl ethanol and maintains the agitation during 48 hours at room temperature. NC dry concentrated under reduced pressure, the residue on silica chromatography, eluted by a mixture hexane ethyl ether (8 - 2) and obtains 250 mg of product

attondu

F.? 59 C..d-α==570 + 20 + (c=0.4% benzene) d the (1r, cis-) 2.2-dimethyl 3 - (Z-)/- 3 oxo 3-chloro-1 a-propenyl/cyclopropane carboxylate of a cyano-OC(O)- 3-phenoxy benzyl used at the start of the example 40 was prepared by the action of thionyl chloride on the (cis-1r) 2.2-dimethyl 3 - (Z-)/3hydroxy-to-3 oxo - 1 a-propenyl/(e) cyclopropanecarboxylic

carbxoylate

of α-cyano - 3-phenoxy benzyl preparation VII below.

Exemole

41: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (L-trifluoro methyl 1 methyl-

propyloxy

) 1 a-propenyl/cyclopropane carboxylate of (e)- α-cyano 3-phenoxy benzyl.900 mg of dissolved (cis-1r) 2.2-dimethyl 3 - (Z-)/3chloro-to-3 oxo - 1 a-propenyl/cyclopropane carboxylate of (e)- α-cyano 3-phenoxy benzyl 3 cm3 in methylene chloride, adds the I cm3 of 1-trifluoromethyl 1-methyl propanol and stirred for 16 hours at room temperature under an inert atmosphere and with the exclusion of

lthumìdité

. After 3 days at room temperature the reaction mixture is washed with a saturated aqueous solution of

soduim

bicarbonate and water, dried and concentrated to dry. The residue on silica chromatography is eluted by a mixture hexane ethyl ether (8 - 2) and 570 mg of expected product is obtained.Example 42 (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2

',

3 a-

dihydroxpropyloxy

) 1 a-propenyl/cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.Heated at reflux 4.65 g of (cis-1r) 2.2-to-

diméthyl3

-/(Z-) - 3 oxo substituted 3 - (2.2-dimethyl

dioxolanyl

substituted 4 - (R) methoxy) 1 a-propenyl/cyclopropane carboxylate of (e) a cyano - 3-phenoxy benzyl (example 37), Dioxane 46 cm3, 9 cm3 0.45 g of water and paratoluene sulfonic acid during 45 min. The majority of the dioxane is removed by distillation at reduced pressure 400c, resumes the residue by 150 cm3 25 cm3 of methylene chloride and water. Agitated, decanted, the organic phase washed with water, dried and concentrated to dry under pressure re

duite.On

chromatography the residue in silica, eluted by a mixture cyclohexane ethyl acetate (3 - 7) and obtains 3.85 g of desired product with d=α + 530 + 2.50 (c=0.5% cecl3) 43 g.: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2 a-

tetrah.y

-

dropyranyloxyéthoxy

) 1 a-propenyl/(R) of the cyclopropane

carbxoylate

α-cyano - 3 a-

ohénoxy

benzol.Step a: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2 a-

tétrahydropyranyloxyéthoxy

) 1 a-

propynyl

or cyclopropane

carbxoylate

/(R)- α-cyano-benzyl 3-phenoxy.Operations are carried out analogously to that described in example 7

stadeA

at, at the start of 2.3 g of (cis-1r) 2.2 - dimethyl-3/(Z-) - 3 hydroxy-3 oxo 1 a-

propynyl

/cyclopropane carboxylate of (R)- α-cyano 3-phenoxy benzyl and 7.5 g of 1 - bromo2 (2 tetrahydropyranyl) oxy-ethane. 1.8 g of product is obtained after chromatography on silica expected in the mixture cyclohexane ethyl acetate (75 - 25).Step b: (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3 and (2 a-

tétrahydropyranyloxyéthoxy

) 1 a-

pyopényl

/

carbxoylate

(R) of the cyclopropane-cyano 3-phenoxy benzyl.Operations are carried out analogously to that described in step b of example 7, starting from the product obtained at

stadeA

di thereon. Is obtained after purification by chromatography in the mixture cyclohexane ethyl acetate (80 - 20), 1.3 g of desired product.9=330 + 10 * (c=1% chcl3) D. - the (cis-1r) 2.2-dimethyl 3 - (Z-)/3 hydroxy - 3 oxo 1 a-

propynyl

/cyclopropane carboxylate of (R) α-cyano 3-phenoxy benzyl used at the beginning of the example earlier been prepared in a manner analogous to that of the ester (e) α-cyano 3-phenoxy benzyl IV enzyme preparation.Example 44: (IR-cis-) 2.2-dimethyl 3 - (Z-)/- 3 oxo substituted 3 - (2 hydroxy ethoxy) 1 a-propenyl/

cycloprocane

carboxylate (R)- α-cyano 3-phenoxy benzyl.0.85 g of mixed product obtained in example 43, 17 cm3 ethanol, 5 cm3 of dioxane, 1 cm3 of water and 4 cm3 2n hydrochloric acid and then stirred at 20 C. for 3 hours. We,, then > 1 cm3 of triethylamine, evaporated to dry, resumes by a mixture of water and ice, extracted by methylene chloride, washing the extract with water, dried and evaporated the solvent. Is chromatography on silica by eluting the

rédidu

mixture cyclohexane ethyl acetate (65 - 35) and 0.65 g of expected product is obtained.d-α=+ + (c=0.5% chcl3) 42.50 + 2.50 the following compounds may also be obtained according to the method of the invention, starting from the corresponding acids and alcohols - (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3. (1.1.1.3.3.3-to-hexa-fluoro-propoxyl) propenyl/cyclopropane carboxylate of 3-phenoxy benzyl.d-α=26.5 + 2.5# (c=0.5% chcl3) - the (cis-1r) 2.2-dimethyl 3 - (Z-)/- 3 oxo - 3. (1.1.1.3.3.3-to-hexa-fluoro-propoxyl) propenyl/cyclopropane carboxylate of (e)- α-cyano 3-phenoxy 4-fluoro-benzyl.d-α==270 + 20 + (c=0.8% benzene).Preparation of IV: (

lR.cis

) 2.2-dimethyl 3 - (3 oxo 3 hydroxy 1

pronynyl

) cyclopropane carboxylate of (e)TDC-cyano-benzyl 3-phenoxy.Step a: (cis-1r) 2.2-dimethyl .3/2 carboxy/ethynyl cyclopropane carboxylate of

terbutyle

: introduced 26 g of (cis-1r) 2.2-to-dimethyl 3 - (2,

2dibromovinyl

) cyclopropane carboxylate of

terbutyle

in 175 cm3 of anhydrous tetrahydrofuran. Then added to a solution of butyl - 650c 60 cm3 lithium at 20% in cyclohexane.1 hour to -60 agitated C and bubbled through a carbon dioxide flow during 1 hour and a half, pouring the mixture in cases tee members corresponding in chilled water added soda n is washed with ether. The alkaline aqueous phase is acidified to pH 4 and extracted with ether. The organic phases are dried, causes dry under reduced pressure. The obtained product is recrystallized in petroleum ether (60 - 800 c to EB). The result is 8.3 g of the desired product melts at 1440 C..NMR cdc13 1.22 ppm of 1.37 and methyls protons 2 cyclopropane 1.78 proton at 1 and 3 1.47 cyclopropane protons of the proton-groupementemi47.1

terbutyle

8.25Step b: (cis-1r) 2.2-to-dimethyl 3 - (2.2.2-to-

trichloroéthoxycarbonyléthylnyll

cyclopropane carboxylate of

terbutyle

.6.2 g of dicyclohexyl carbodiimide is introduced into a solution containing 7.15 g of (cis-1r) 2.2-to-dimethyl 3 - (

2carboxyéthynyl

) cyclopropane carboxylate of 80 mg of dimethylaminopyridine

terbutyle

and 35 cm3 in methylene chloride.The reaction mixture was stirred for 10 minutes and added 4.5 g of 2.2.2-to-trichloroethanol. Is maintained under stirring for one hour and eliminates by filtration the precipitate formed.The filtrate is washed with n hydrochloric acid and then with water until neutrality, the dry and causes it to dry. Obtained 14 g of an oil which is chromatographed on silica by eluting the benzene ethyl acetate (97 - 3). Thus isolated 9 g of the desired product melts at 70 - 710 C..Step c: acid (cis-1r) 2.2-to-dimethyl 3 - (2.2.2-to-

trichloroéthoxycarbxoyl

ethynyl) cyclopropanecarboxylic acid.It refluxes for one hour a mixture containing 11.4 g of the product prepared according to step b, 120 cm3 toluene and 300 mg of paratoluene sulfonic acid. Allowed to return to room temperature, the reaction mixture is washed with water, dried, and causes it to dry. This provides 9.5 g of the desired product is used as such for the next step.Step d: (cis-1r) 2.2-to-dimethyl 3 - (2.2.2 4N-trichloro ethoxy

carbxoyl

ethynyl) (e) or cyclopropane

carbxoylate

of α-cyano - 3-phenoxy benzyl.6.2 g of

dicyclophexylcarbodiimide

is added in a solution containing 9.5 g of the product prepared in step c, 30 cm3 3 cm3 of methylene chloride and pyridine. The reaction mixture was stirred for half an hour and adds 6.8 g of alcohol (e) α-cyano-benzyl 3-phenoxy. Is maintained under stirring for one hour and a half. Is removed by filtration, the insoluble formed. The filtrate is washed with n hydrochloric acid and then with water until neutrality. Dried, the filter and causes it to dry. Obtained 16.3 g of an oil which is chromatographed on silica by eluting the mixture (97 - 3) ethyl Benzeneacetate. Thus isolated 12 g of the desired product melting at 101 C..Step e: (cis-1r) 2.2-to-dimethyl 3 - (3 hydroxy 3 oxo 1 a-

propynyl

) cyclopropane carboxylate of (e) α-cyano-benzyl 3-phenoxy.5.9 g of powder is introduced zine derivatives in a solution of 6.5 g of the product prepared in step d, 23.4 cm3 2.6 cm3 acetic acid and water. The mixture is maintained under stirring for one hour. Is filtered and settle upon the filtrate. The organic phase is washed with water and extract the aqueous phase to methylene chloride. One joins

chlorométhylériques

solutions, dried, the filter and causes them to dry. This gives 4.7 g of crude product used as is.Preparation of V: (cis-1r)/2.2-to-dimethyl 3 - (Z-) ' (3 hydroxy 3 oxo 1 a-propenyl/

terbutyle

cyclopropane carboxylate of hydrogen is 2 g of (cis-

îR

) 2.2-dimethyl .3/2 carboxy/ethynyl cyclopropane carboxylate of

stadeAterbutyle

prepared at 40 cm3 IV in the preparation of ethyl acetate in the presence of 0.38 g of 10% palladium hydroxide on barium sulfate and 0.4 cm3 of

quinolélne

is filtered ., washing the filtrate to 0.5 n-hydrochloric acid and then with water until neutrality, dried, concentrated to dry under reduced pressure and obtains 2 g of the desired product melts at 940 C..Preparation IV: @ ' acid (cis-1r) 2.2-to-dimethyl 3 - (Z-)/3 oxo - 3. (-2 (1.1.1.3.3.3 hexafluoroisopropyl) propoxyl) cyclopropanecarboxylic acid/1 a-propenyl.Step a: (cis-1r) 2.2-to-dimethyl 3 - (Z-)/3-oxo-substituted 3 - (or 2 - (1.1.1.3.3, 3:00

exafluoro

propoxyl) 1 a-propenyl/

carbxoylateterbutyle

of the cyclopropane.Operation is carried out as in step a of example 9, 3.6 g of usable in heterozygous (cis-1r) 2.2-to-dimethyl 3 - (Z-)/3 hydroxy 3 oxo 1 a-propenyl/

terbutyle

cyclopropane carboxylate of (V-preparation) and 3 g of the hexafluoro-isopropyl alcohol. After elution from a mixture: (4 - 6) benzene-cyclohexane derivatives obtained 4.9 g of desired product c-f=92.Step b: acid (cis-1r) 2.2-to-dimethyl 3 - (Z-)/3-oxo-substituted 3 - (or 2 - (1.1, 1.3.3.3-to-hexafluoropropylene) propoxyl) cyclopropanecarboxylic acid/1 a-propenyl.Operation is carried out as to the example 11 step b, from 4.9 g of the product obtained above and obtains 4.2 g of desired product.

EMI49.1

AN IR <SEP>

CHCl

<tb> AN IR <SEP> CHC13)<tb> THE OH <SEP> acid <SEP> single <SEP> 1 <SEP> 3500 <SEP> cms-a 1<tb> <SEP> + <SEP> digests<tb> the ester <SEP>

conj

<SEP> grams <SEP> 1755 <SEP> cms-a 1 <SEP> shoulder<tb> <SEP> 1744 <SEP> voter <SEP> max.<tb> <SEP> acid <SEP> 1695 <SEP> cms L<tb> <SEP> IC <SEP>

conj

<SEP> 1627 <SEP> cms L<tb> <SEP> gEMs. <SEP> dimethyl <SEP> 1380 <SEP> cms L <SEP> shoulder<tb>

Préoaration

living area: (cis-1r) 2.2-to-dimethyl 3/(Z-) 3 hydroxy 3 oxo 1 a-propenyl cyclopropane carboxylate of (e) a cyano - 3-phenoxy benzyl.4.7 g of hydrogenated (cis-1r) 2.2-to-dimethyl 3 - (2carboxy ethynyl) cyclopropane carboxylate of (e) a cyano - benzyl-O <

3phénoxy

45 cm3 (preparation of IV) in ethyl acetate in the presence of 500 mg of 10% palladium hydroxide on barium sulfate and 6.5 cm3 quinoline. Is filtered, washing the filtrate to the n hydrochloric acid, then with water until neutrality, dry and causes dry. Obtained 5.1 g of an oil which is chromatographed on silica by eluting the mixture of hexane, ethyl acetate, acetic acid (70 - 30 - 1). This gives 3.8 g of the desired product.Preparation VIII-:: (cis-1r) 2.2-to-dimethyl 3 - (Z-)/3 hydroxy 3 oxo/1 a-propenyl or cyclopropane

carbxoylate

of α - (R-) methyl 3-phenoxy benzyl.Step a: (cis-1r) 2.2-to-dimethyl 3 / - 3 oxo - 3 and (2.2.2 4N-trichloro ethoxy) propynyl/cyclopropane carboxylate of methyl α - (R-) 3-phenoxy benzyl.Operation is carried out as in step d of the preparation VI, using 6 g acid (cis-1r) 2.2-to-dimethyl 3 / - 3 oxo - 3 and (2.2.2 - trichloroethoxy) propynyl/cyclopropane carboxylic and 4.1 grams of1 - (R.) (- 3-phenoxy phenyl) ethanol. Obtained after chromatography in a cyclohexane - ethyl acetate (8 - 2), 4.38 g of desired product.Step b: (cis-1r) 2.2-to-dimethyl 3/3 oxo - 3 hydroxy-propynyl/cyclopropane carboxylate of (the R) α-methyl 3-phenoxy benzyl.Has 4.16 g of product obtained above 4 cm3 dissolved in methylene chloride is added 10% acetic acid to 45 cm3 water and 0.53 g of zinc powder and stirred 30 minutes at room temperature, 0.53 g of refilled zinc powder upto end of reaction (4 times). After 3 hours of contact is filtered and extracted by methylene chloride. The organic phase is washed with water, dried, concentrated by dry toluene and obtains training azeotropic 2u 3.05 g of desired product.Step c: (cis-1r) 2.2-dimethyl substituted 3 - hydroxyl/(Z-) 30 3 oxo 1 Pro

pényl

/cyclopropane carboxylate of methyl α - (R-) 3-phenoxy

benovle

.Operation is carried out as in step b of example 7, starting from the product obtained in step b above and obtains 2.9 g of crude desired product, used as such.

ExemDles

of

ComsositionsExemDle

has: preparation concentrate.Mixed homogeneously

deProduit

of the example 1.............................. 0.25

gButoxyde

piperonyl........................ 1

gTween

80......................................... 0.25

gTopanol

has................................ 0.1

gEau

................................. 98.4

gExemple

b.: preparation of an emulsifiable concentrate.In the example

intimementProduit

mixed 1........................... 0,015

gButoxyde

piperonyl............................ 0.5

gTopanol

has............................ 0.1

gTween

80............................. 3.5

gXylène

............................... 95,885 grams e.g. C:: preparation of an emulsifiable concentrate.Mixed homogeneously

deProduit

of the example 1..................... 1.5

gTween

80................................ 20

gTopanol

has................................. 0.1

gXylène

............................ 78.4

gExemple

'd: preparation of a smoke composition.A homogeneously mixed product of the example 1........................ 0.25

gPoudre

of

tabu

........................... 25

gPoudre

of cedar................... 40

gPoundre

pine wood......................... 33.75

gVert

gloss.................................. 0.5 grams of P-nitrophenol.................................... 0.5

gEtude

activity of compounds of the invention on pests.1): study of the lethal effect on

domesticues

flies.Insects tests are flies domestic female 4/5 days of age. It is performed by topical application of 7 L solution

acétonicue

product on dorsal thorax insects by the micro-manipulator of Arnold. NC uses 50 individuals per dose and processing. We monitor mortality twenty-four hours after treatment.The result expressed DL 50 or dose (in nanograms) necessary to kill 50% of the insects, emi51.1 is as follows<tb> Product <SEP> of <SEP> : <SEP> LID <SEP> 50<tb> the example <SEP> : <SEP> (nanograms <SEP> by <SEP> individual)<tb> <SEP> 1 <SEP> : <SEP> 1,115<tb> <SEP> 23 <SEP> : <SEP> 0,962<tb> <SEP> 29 <SEP> : <SEP> 0,825<tb> Concluding: on the test used, the products of examples 1, 23 and 29 have a remarkable activity.20): study of the effect on

Stodotteralittoralis

larvae.The assays are performed by topical application of a solution of the ketone product to be tested by the micro-manipulator of Arnold on dorsal thorax larvae. 15 used larvae per dose of product to be tested. The larvae used are larvae of the fourth larval stage,

c'est

to say about 10 days

âgéees

when grown to 240c and 65% relative humidity. After treatment, the individuals are placed on an artificial diet (

Poitout

medium).We monitor 48 hours after treatment of mortality.The experimental outcome obtained is the suivantemi52.1<tb> <SEP> Compound <SEP> of <SEP> : <SEP> LID <SEP> 50<tb> <SEP> the example <SEP> : <SEP> (nanograms <SEP> by <SEP> individual)<tb> 1 <SEP> : <SEP> 4,699<tb> <SEP> 35 <SEP> : <SEP> 0,544<tb> Concluding: on the test used, the products of the examples 1 and 35 have a good activity.3): study of the activity of shock on housefly.Insects tests are flies domestic female 4/5 days of age. It is performed by direct spraying in chamber Kearns and market by using as solvent a mixture in equal volumes of acetone and L-

isopar

(amount of solution used 2 x 0, 2 cm3). NC uses about 50 insects by treatment dose. Checks are carried out every minute to 10 min, and then 15 minutes and it is determined the KT 50 by the usual methods.The results obtained are as follows emi53.1<tb> Product <SEP> of <SEP> ORIGIN <SEP> 50 <SEP> Concentration Of<tb> the example <SEP> in <SEP> min <SEP> g/l<tb> <SEP> 1 <SEP> 3,534 <SEP> 1<tb> <SEP> 2 <SEP> 3,608 <SEP> 0.25<tb> <SEP> 26 <SEP> 1,550 <SEP> 0.25<tb> <SEP> 30 <SEP> 3,498 <SEP> 1<tb> <SEP> 35 <SEP> 2,894 <SEP> 1<tb> Concluding: on the test used, the products of examples 1, 2, 26, 30 and 35 have a good activity.40): study of the abovementioned tar activity contacting

tarsal

on German cockroach, (compound of the example 1) insects tested are males of German cockroach (

BlaLellaermanica

@). It is performed by depositing a ketonic solution of predetermined concentration on the bottom of a petri dish of 20 cm in diameter. After drying is allowed dwell 20 male cockroaches by concentration during 1 hour are transferred insects on medium healthy and checked their mortality to 24 hr, 48 hr, 3 and 5 days.The result expressed lethal concentration (LC 50) 50 gives, for the product in question, 0,216 mg/m2.Concluding: as judged used the product exhibits very good activity.5);:

Tétranvchus

activity on the authorisation. (compound of the example 1)

adultioide

test plants are used bean KOM, carrying two cotyledonary leaves. These plants are treated at gun Fisher method with an acetone solution of the product. After comstically rim 25 female acarid

Tétranychus

authorisation of noses are asked of sheets either 50 individuals per dose experienced by PI=T-. Efficacy controls are performed after the I, 24, 48 and 72 hours of contact.To the dose of 2.8 mg/L being the product exhibits very good activity.