Process of transformation of an ester of secondary chiral alcohol acid - cyané optically active of structure (R) out of ester of chiral acid of secondary alcohol - cyané of structure (S), products and compositions insecticidal.

The present invention relates to a method of transforming an ester of chiral acid secondary alcohol-cyané, optically active structure (the R) acid ester to a chiral secondary alcohol this~cyané structure (e).

SUBSCRIBES^- invention relates to a method of transforming a

, chiral acid ester (has) alcohol (d) optically active structure (the R) or racemic structure (the R, O), of formula b:

or a blend of non-equimolar, chiral acid ester (has)'d ' alcohol (d) optically active structure (the R) having a particular chiral acid (has) alcohol (d) optically active structure (e), mixture designated by "ester of (r + s)", ester to a chiral acid (has) alcohol (d) optically active structure (e), characterized in that the ester of subjecting chiral acid (has) alcohol (d) optically active, of "structural (R.), or racemic (R-, e), or the mixture of esters called" ester of (r + s) ", to the action of a basic agent selected from the group consisting 1 * ammonia, primary amines, secondary amines, tertiary amines, quaternary ammoniums, the ion exchange resins with basic character, amines high-molecular weight liquid and strong bases which, they, are used in a catalytic amount, within a solvent or mixture of solvents in which the ester of chiral acid (has) alcohol (d), (e) structure is insoluble and the ester of chiral acid (has) alcohol (d) structure (the R) is soluble, and then isolated from the reaction medium, the ester of chiral acid (has) alcohol (d) structure (E) thus insolubilized.

This method will be hereinafter referred to as a, general method has '.

The invention particularly relates to a method of transforming an ester of chiral acid (has) alcohol (d) optically active structure (the R) or racemic structure (the R, O), of formula (d):

or a mixture, in proportion not équintoléculaire, chiral acid ester (has) alcohol (d) optically active structure (the R) having a particular chiral acid AC) alcohol (d) optically active structure; (e) mixture designated by " ester of (r + s)'¹ , ester to a chiral acid

(Has) alcohol (d) optically active structure (e), characterized in that the ester of subjecting chiral acid (has) alcohol (b.) throughput opti■expressions of active, structural (R.), or racemic (R-, e), ' drinking the mixture of esters said^,, the ester (r + s)^M , to the action of a basic agent selected from the group consisting of ammonia, secondary amines, tertiary amines, and strong bases which, they, are used in a catalytic amount, within a solvent or mixture of solvents in which the ester of chiral acid (has) alcohol {d}, (e) structure is insoluble, and the ester of chiral acid (has)^; alcohol (d) structure (the R) is soluble, and then isolated from

reaction *, 1' chiral acid ester (has) alcohol (d) structure

This method will be hereinafter referred to as a, general method has.

The chiral acid (has) may be an acid having an atom

asymmetric carbon *

The invention proposes a method conforming to the general method has * and especially according to the general method a and characterized in that the chiral acid is an acid having an asymmetric carbon.

The chiral acid (has) can also be an acid having two asymmetric carbon atoms, such as cyclopropane carboxylic acid wherein two of the ring carbons are asymmetric.

The invention proposes a method conforming to the general method has' and especially according to the general method has, characterized in that the chiral acid (has) is an acid having two asymmetric carbon atoms and more particularly to a cyclopropane carboxylic acid of which two of the ring carbons are asymmetric carbons.

The chiral cyclopropanecarboxylic acid (has) is preferably an optically active cyclopropane carboxylic acid of cis form or trans:

wherein Hal is chlorine or bromine.

In the following text, according to a simplified nomenclature

•adopted recently, acids of structure (1r, DY) may be called acids (1r, the cis).

Among the preferred chiral cyclopropanecarboxylic acids

of the invention, these included:

- acid 2.2-dimethyl 3r * ' (2.2 to-dibromovinyl) cyclopropane 1rcarboxylic 1r or acid, the cis 2.2-dimethyl 3 (2.2 to-dibromovinyl) cyclopropanecarboxylic, _

- 1' acid 2.2-dimethyl 3r * - (2.2 above dichlorovinyl) cyclopropane 1rcarboxylic rpm or acid, the cis 2.2-dimethyl 3 (2.2 to-âichlorovinyl) cyclopropanecarboxylic acid.

the basic agent used in the method of the present invention has generally, which is performed in the presence of the ester of the chiral acid (has) and alcohol (d) optically active structure

(Û), or racemic structure (the R, O) or the mixture, in proportion non-equimolar, chiral acid ester (has) alcohol (3) structure (the R) having a particular chiral acid (has) alcohol (d) (e) structure, in chiral acid ester (has) and alcohol (d) (e) structure, is, preferably, selected from the group consisting of ammonia, tri ethyl amine, diethylamine, morpholine, pyrrolidine, piperidine, used in a catalytic amount, soda, potash, the alkali alcoholates, amides the alkali, alkali hydrides.

This list of bases used preferably in the method of the present invention has, without limitation. Other databases like force could be used without departing from the scope of 1' disclosure.

Among these bases, include those selected from the group consisting of isopropylamine, ephedrine, triethylene diamine derivatives■, ter-potassium butoxide and 1¹ sodium isopropoxide, these last two bases being used in a catalytic amount.

Among these basic agents 1' triéthylsmine or ammonia are used in a particularly advantageous manner.

The I "' basic agent used in the method generally has' of the present invention is, preferably, selected from the group consisting of ammonia, triethylamine, diethylamine, morpholine, pyrrolidine, piperidine, and, used in a catalytic amount, soda, potash, the alkali alcoholates, the alkali amides, alkali hydrides.

This list of bases used preferentially in the method of the invention, without limitation. Other databases like force could be used without departing from the scope of the invention.

Among these bases, include those selected from the group consisting of isopropylamine, ephedrine, triethylenediamine, ter-potassium butoxide and 1 * isopropylate of ' Na, these last two bases being used in a catalytic amount.

Basic agent, according to the general method has ', can also be used benzylamine, n-butylamine, sec-butylamine, tetra-butyl ammonium hydroxide.

The basic agent•used may also be an ion exchange resin, a strong basic character comprising quaternary ammonium compounds or amines.

By Dow mal. sells such basic agents under the name of "DOWEX" and dealer sells and Haas replication or the like under basic agents herein as "AMBERLITE '".

These commercial products are advantageously used as basic agents in the method<the X ' of the invention.

Can be, for example, invoke the DOWEXAGIX8 or at Amber introducing new 400 will 45 or IR.

The basic agent used may also be an amine with a high molecular weight water-insoluble.

The company replication and Haas commercialized under the name of "liquid AMBSRLITE"_{the R} - products which can be usefully employed as basic agents according to the method has' of the invention.

This is how we can use the AliBERLITES m1 la2 or liquid type.

The solvent or mixture of solvents used in the process of X *<, and particularly in the method has, is advantageously selected from the group consisting of 1 'acetonitrile derivative, alkanols, and mixtures of alkanol and petroleum ether, in particular mixtures of alkanol and pentane, hexane or heptane and more particularly from the group consisting 1' acetonitrile derivative, propanol, 1 * of isopropanol, isobutanol the linear and branched alcohols and mixtures of the foregoing with gasoline grams, b-gasoline, petrol C, petrol E, pentane, 1 'hexane or 1' heptane derivatives "

The L * isopropanol is particularly useful for producing the conversion according to the methods of the invention.

II is well evident that the terms "insoluble" for the alcohol esters of structure (e) and "soluble" for the alcohol esters of structure (I) are taken in their ordinary meaning. In solvents useful in the methods of the invention, the alcohol esters of structure (e) have a certain solubility, which must be sufficiently low efficiency is good, considering the volume of solvent used.

In practice, the solvents or mixture of solvents used as well as the volumes of these solvents used, throughput can be obtained weight in alcohol ester of structure (e) of at least 80%. The list of solvents or mixture of solvents, mentioned hereinbefore, does-not of limitation. Other solvents or mixture of solvents could be used without departing from the scope of the invention.

The alcohol esters of structure (the R) are, in general, high solubility in the solvents used in the methods of the invention and a small volume of solvent allows them to completely solubilize.

The reaction temperature affects the reaction rate.

The reaction time is function, in particular, temperature and also the nature of the base used.

Among the chiral acids (has) cyclopropane carboxylic type, the acids of more highly preferred is acid 2.2-dimethyl 5r (2.2 to-dibromovinyl) - cyclopropanecarboxylic acid or 1r 1r-carboxylic acid, 3 - cis-2.2-dimethyl (2.2 to-dibromovinyl) cyclopropanecarboxylic acid.

The invention therefore provides a method according to the general method (and *) transformation of an ester acid 2.2-dimethyl 3r - (2.2~dibromoviny1) cyclopropanecarboxylic~1r-carboxylic α-cyano alcohol 3 a-phenoxybenzyl, optically active structure (the R) or racemic structure (the R, e) of the formula (d):

or. a mixture, non-equimolar ratio, of 2.2-dimethyl 3r (2.2 to-dibromovinyl) - cyclopropane 1r-carboxylate (R.) α-cyano, 3 a-phénoxÿbenzyle and j-R->2.2-dimethyl - (2 ., 2 a-dibromovirdibromovir.yl) cycloprcpane-to-1r-carboxylate (e) α-cyano 3 a-phénoxybenzyle, mixture designated by "-bromo ester of (r + s)", in 2.2-dimethyl 3r (2.2 to-dibromovinyl) - cyelopropane-to-1r-carboxylate (e) α-cyano 3 a-phénoxybenzyle, characterized in this subjecting the ester of optically active alcohol of structure (R.), the ester of racemic alcohol of structure (the R, O), drinking the mixture called " ^ r + s-bromo esters)¹¹ ? previously defined,, to the action of a basic agent, selected from

the group consisting of ammonia, primary amines, secondary amines, tertiary amines, quaternary ammoniums, the ion exchange resins with basic, amines high-molecular weight liquid and strong bases which, they, are used in a catalytic amount, within a solvent or mixture of solvents in which the 2.2-dimethyl 3b (2.2 to-dibromovinyl) - cyclopropane-IR-carboxylate (e) α-cyano 3-phenoxy benzyl is insoluble, and wherein the 2.2-dimethyl 3r (2.2 to-dibromovinyl) - cyclopropane 1 'R-carboxylate (β) α-cyano 3-phenoxy benzyl is soluble, and then isolated from the reaction medium the alcohol ester of structure (e), thereby insolubilized, called β method¹ .

The invention particularly relates to a method conforming to the general method (has) transformation of an ester acid 2.2-dimethyl 3r (2.2 to-dibromovinyl) - cyclopropane-IR-carboxylic α-cyano alcohol 3-phenoxy benzyl, optically active structure (e) or racemic structure (the R, e) of the formula (d):

or a mixture, non-equimolar ratio, of 2.2 to-substituted dimethyl 3r (2.2 to-dibromovinyl) - cyclopropane 1r-to-cârboxylate of α-cyano (K.) 3 a-phénoxybenzyle and 2.2-dimethyl 3r - (2.2 to-dibromovinyl} cyclopropane 1r-carboxylate (e) α-cyano 3 a-phénoxybenzyle, mixture designated by "-bromo ester of (r + s)", in 2.2-dimethyl 3 - Η (2.2 to-dibromovinyl) cyclopropane 1r-carboxylate (e) α-cyano 3 a-phénoxybenzyle, characterized in that the ester is subjected of optically active alcohol of structure (R.), the ester of racemic alcohol of structure (the R, O}, drinking the mixture called "-bromo ester of (r + s)^{the n} , previously defined, to the action of a basic agent, selected from the group consisting of ammonia, secondary amines, tertiary amines ., and strong bases which, they, are used in a catalytic amount, 'within a solvent or mixture of solvents in which the 2.2-dimethyl 3r U-shapes, 2 a-bromo vinylaromatic) cyclopropane 'lR-carboxylate (e) α-cyano 3-phenoxy benzyl is insoluble, and wherein the - 2.2-dimethyl 3r (2.2 to-dibromovinyl cyclopropane infrared-carboxylate (R.) α-cyano 3-phenoxy benzyl is soluble, and then isolated from the reaction medium the alcohol ester of structure (e), thereby insolubilized, called β method.

For performing the processing of alcohol ester - optical, centeredly active structure (I), racemic alcohol ester (the R, O) or mixing, in proportion non-equimolar alcohol esters of optically active ester of optically active alcohol of structure (e) according to the method β¹ and especially the β method described above, the alkali agent and the solvent or solvent mixture used preferably are identical to the basic agents and solvents mentioned above for the methods has' and has.

present invention * hr has more specifically relates to a method in accordance with the method of the β transformation 2.2-dimethyl 3r (2.2 to-dibromovinyl) - eyelopropane-to-LP-carboxylate (R.) α-cyano - 3 a-phénoxybenzyle in 2.2 * 4 iméthyl 3r (2.2 to-dibromoviny 1) cyclopropane 1. of R-carboxylate (E) α-cyano 3 a-phénoxybenzyle, characterized in that

- submits the ester of optically active alcohol of structure (the R) to the action of a, basic agent selected from the group consisting of 3 _ 'ammoniaquej secondary amines, tertiary amines, and strong bases which, they, are used in a catalytic amount, within a solvent selected from the group consisting of 1' acetonitrile derivative_O alkanols, and mixtures of alkanol and petroleum ether, in particular mixtures of alkanol and pentane, hexane, or d¹ to heptane, called ^ method and more particularly to a method according to method T wherein the basic agent is ammonia or triethylamine and the solvent is isopropanol.

The invention also relates to a method according to method P-' characterized in that, the reaction is carried out at the start of the ester of optically active alcohol of structure (R.), t'a method called₀

The invention more particularly relates to a method according to method β transformation 2.2-dimethyl 3 - Ε (2.2 to-dibromovinyl) cylopropane and 1 the R-carboxylate (the R, O) α-cyano 3 a-phénoxybenzyle in 2.2-dimethyl 3r - (2.2 to-dibroniovinyl) cyclopropane 1r~earboxylate of (e) α-cyano 3 a-phénoxybenzyle, characterized in that subjects the racemic alcohol ester, to the action of a basic agent selected from the group consisting of ammonia, secondary amines, tertiary amines, and strong bases, which, they, are used in a catalytic amount, within a solvent selected from the group consisting of 1' acetonitrile derivative, the.

alkanols and mixtures of alkanol and petroleum ether in particular mixtures of alkanol of pentane and hexane or heptane, in particular a method called cTet method according to method (T wherein the basic agent is ammonia or triethylamine and the solvent is isopropanol.

The invention also relates to a method according to method β ^ characterized in that the reaction is carried out at the start of the racemic alcohol ester, FS method called '.

the invention also relates to a method according to method β transformation of a blend of non-equimolar 2.2-dimethyl 3>R. (2.2 to-dibromovinyl) - cyclopropane 1 the R-carboxylate (R.) α-cyano 3 a-phénoxybenzyle and 2.2-dimethyl 3r (2.2 to-dibromovinyl) - cyclopropane 1r-carboxylate (e) α-cyano 3 a-phph.énoxybenzyle in 2.2-dimethyl 3r - (2.2 to-dibroraovinyl) cyclopropane 1Rearboxylate of (e) α-cyano 3 a-phénoxybenzyle, characterized in that the ester mixture is subjected to the action of a basic agent selected from the group consisting of ammonia, secondary amines, tertiary amines, and strong bases which, they, are used in a catalytic amount, auau.sein of a solvent selected from the group consisting of 1' acetonitrile derivative, alkanols, and mixtures of alkanol and petroleum ether, in particular mixtures of alkanol and pentane, hexane had heptane, and £referred more particularly to a method according to method of £characterized in that, the basic agent is ammonia or triethylamine and the solvent is isopropanol.

The invention also relates to a method according to method β ·, characterized in that the reaction is carried out at the start of the mixture called "-bromo ester of (r + s)", method called.

the invention also relates to a method, according to the process has, for transforming an ester of 2.2-dimethyl j3b - (has, 2 a-dichlorovinyl) cyclopropane 1 R carboxylic'd ' α-cyano alcohol 5" - phenoxy benzyl, optically active, structure (the R) or R; jcômiq_ue structure (the R, O), of formula:

(B.)

or a blend of non-équiinoléculaire 3r 2.2-dimethyl - (2.2 above dichlorovinyl) cyclopropane 1r-carboxylate (R.) α-cyano 3 a-phénoxybenzyle and 2.2-dimethyl 3r - (2.2 above dichlorovinyl) cyclopropane 1 R because boxy ETL of α-cyano (e) 3 a-phénoxybenzyle, mixture designated by " di-chloro-ester (r + s) ', in 2.2-dimethyl 3r - (2.2 above dichlorovinyl) cyclopropane 1r-carboxylate (e) α-cyano 3 a-phéncxvbenzyle, characterized in that the alcohol ester is subjected to optical telling. active structure (R.), the alcohol ester raceraic (the R, O) or mixture called " di-chloro-ester (r + s ^, to the action of a basic agent selected from the ' group consisting of ammonia, secondary amines, tertiary amines, and strong bases which, they, are used in a catalytic amount, in a solvent or mixture of solvents in which the 3r 2.2-dimethyl - (2.2 to-dichiorovinyl) cyclopropane-IR-carboxylate (e) α-cyano 3 a-phénoxybenzyle is insoluble and wherein the 3r 2.2-dimethyl - (2.2 above dichlorovinyl) cyclopropane ir-carboxylate (R.) α-cyano 3 a-phénoxybenzyle is soluble, and then isolated from the reaction medium the alcohol ester of structure (e), thereby insolubilized, the process called β ^.

The invention also relates to a method according to the process has ^ *, characterized ' in that the chiral acid (has) is acid 2.2-dimethyl 3r - (2.2 above dichlorovinyl) cyclopropane-to-1r-carboxylic, β method called¹ ^.

The basic agent and the solvent or solvent mixture used preferably in the β method¹ ^ ^ β and particularly the method are identical to the basic agents and solvents mentioned above for the methods, has' and has.

The invention also relates to a method according to method transforaatien β ^ of the 2.2-dimethyl 3r - (2.2 above dichlorovinyl) cyclopropane 1r-carboxylate (R.) α-cyano 3 a-phénoxybenzyle in.

2.2 - dimcthyl 3r - (2.2 above dichlorovinyl) cyclopropane 1 the R-carboxylate (3) α-cyano 3 a-phénoxybenzyle, characterized in that the ester is subjected of optically active alcohol of structure (the R) to ' the action.

a basic agent selected from the group consisting of 1 'ammoniacu-to-theS secondary amines, tertiary amines, and strong bases which, they, are used in a catalytic amount, within a solvent selected from the group consisting of 1' acetonitrile derivative, alkanols and mixtures of alcanoj. and petroleum ether, in particular mixtures of alkanol and pentane, hexane or heptane, called method.

In a preferred embodiment of the method, the basic agent is ammonia or triethylamine and the solvent is 1' isopropyl alcohol.

The invention also relates to a method according to method characterized in that the reaction is carried out at the start of the ester of optically active alcohol of structure

(R.), method called the Y ^ '.

The invention also relates to a method according to method 3 -,, transformation of 2.2 to-diraéthyl 3r - (2.2 above dichlorovinyl) cyolo-propane ir-carboxylate (the R, O) α-cyano - 3 a-phénoxybenzyle in 2.2 - dimethyl 3r (2.2 above dichlorovinyl) cyclopropane 1h-carboxylate (e) α-cyano 3 a-phénoxybenzyle, characterized in that subjects the racemic alcohol ester (the R, O) to the action of a basic agent selected from the group consisting of ammonia, secondary amines, tertiary amines, and strong bases which, they, are used in a catalytic amount, within an organic solvent selected from the group consisting of acetonitrile, alkanols and mixtures of alkanol and petroleum ether, in particular mixtures of alkanol and pentane, hexane or heptane, called method.

In a preferred embodiment of the method 5^the basic agent is ammonia or triethylamine and the solvent used is 1' isopropyl alcohol.

The invention also relates to a method according to process b '_1} characterized in conducting the transformed -

except at the start of the racemic alcohol ester (the R, O), method^I called /' ^.

05636 An ' a-a-procédéprocédé.de -, transforming, according to method β ^, a proportioned blend of non-equimolecular 2.2-dimethyl - 5th (2.2~dichlorovinyl) cyclopropane-boxy - 1 H because the Te (the R) α-cyano 3 a-Phe NOx b. them y1e and

5 (2.2-dimethyl j5r - (2.2 above dichlorovinyl) cyclopropane 1 - R.

(e) carboxylate-cyano-3 a-phénoxybensyle, in 2.2-dimethyl RA (2.2 to-diclilorovinyl) - cyclopropanecarboxylic 1r processes or boxy ETL of α-cyano (e) 3 a-phph.énoxybenzyle, mixture designated by " di-chloro ester of the R + ^ ÜJ, characterized in that the ester mixture is subjected to the action

**•0. a basic agent selected from the group consisting of ammonia secondary amines, tertiary amines and strong bases which, elleselles.sont used in a catalytic amount, within a bare organa solvent selected from the group consisting of 1' acetonitrile derivative, alkanols, and mixtures of alcohol and ether

15 oil, in particular mixtures of alkanol, pentane, hexane

or heptane, called method of £.•'

! In a preferred embodiment of the method of £. J., - basic agent is ammonia or triethylamine and the solvent is isopropanol.•

2Û the invention also concerns a method according to method characterized in that, at the start of the transformation to said mixture "(r + s) di-chloro-ester", method called the £ '_V.

Can be given of the mechanism of the method of the invention,

25 the following explanation:

... By the action of a base CTEs strength correctly and which, in practice, is. selected from the group 'consisting of ammonia, the amine I -' primary, secondary amines, tertiary amines, the

quaternary askoniums, ion exchange resins to CHAR-30 tère basic, amines and high-molecular weight liquid

the solid bases, used in a catalytic amount, the ester^{the R} chiral acid (has) of optically active alcohol of structure (the R) contained in the starting material, gives rise to a carbanion CE-cyané resulting in the racemization of the corresponding carbon * 35 the protonationiii^, &|riéûre. confectioneries. ^ within a solvent or Im - mth

laoge then takes for the solvent. soluble fraction, the ΐ: ¾. forming in proportion; ' éouimoléculâire. both: diastéréoiscmères/ester (e) and ester alcpol confectioneries' alcohol, {R-)/according to the scheme:

The intermediate formation of mixture of alcohol ester (e) and alcohol ester (R.) in proportion équimoléeulaireDtro can.

highlighting is evaporating dry tensile is soluble. The process of racemization occurs with a proposed in the practical efficiency. quantitative when, unlike the case of 3. with present invention, there is used a solvent or mixture of solvents in which 3.' alcohol ester (e), the alcohol ester (R.) and the ester of racemic alcohol are soluble•*

This theoretical explanation of the method of the invention, although it aware of all the facts observed is given, of course, as the natural ' illustrative and does not limit the scope of the invention.

the method of 1' present a particularly unexpected because it had not hitherto existed, for so far as is known, of transforming method optically active alcohol ester, ester of optically active alcohol of structure-podal, near quantitative yield. -

the method of the invention is particularly advantageous when the chiral acids used are the cyclopropane because boxy IOL toff optically active R-structure 1, jLT would (or IR, the cis), of the formula:

in which Z is-a bromine atom " or a chlorine atom.

The BN several years of insecticidal compounds have potent activity exceptionally high were prepared through chiral acids previously cited by alcohol 3-phenoxy-cyano-benzyl.

11 has been found further that, generally, the esters of the foregoing chiral alcohol O-cyano-optically active benzyl 3 a-phcnoxy structure (e), have insecticidal activity much higher than corresponding esters of racemic alcohol (the R, O) or optically active structure (R.).

Gold, a cyano alcohol of Cx ^ 3-phenoxy benzyl is synthetically obtained as a racemic compound. The fragility of its molecule, moreover, does not allow resulting in the stereoselective preparation of enantiomers, nor a resolution of the racemic alcohol.

To obtain the alcohol esters of structure (e) cyclopropane carboxylic acids previously cited chain dibrono or dichlorovinylic, the only known method was to effect a separation of the alcohol ester of structure (the R) ester and the alcohol of structure (e) by insolubilizing selective thereof, a suitable solvent date stones, which meant that to mediocre efficiency, necessarily less than 50 ^C. the O / with respect to racemic 1 * ester used.

The alcohol ester (R.) or mixtures of alcohol ester (R.)

and d * (e) alcohol ester, ester-rich alcohol (the R) from thus preparing the ester alcohol (sec.), then appeared as residues under performing the preparation of the esters (e)* alcohol.

the method of the present invention can now be directly convert near quantitative yield either esters cyclopentan-I - 2.2 to-diméthy1 3r (2.2 to-dibromoviny1) cyclopropane 1 R carboxylic or 2.2 to-àiméthyl 3r - (2.2 to-dichloroviryi) cyclopropane 1 R carboxylic alcohol 3-phenoxy-cyano-benzyl, racemic of structure R, e, is the alcohol esters of strusture (R-•) of these acids, or mixture of alcohol esters of structure (the R) and alcohol of structure (e), non-equimolar ratio, and specially the ester mixtures rich in ester alcohol * (R.), in alcohol ester of structure (e), near quantitative yield.

The method of the invention comprising only one stage, involving simple manipulations and using inexpensive reagents, results in very high yield in particularly advantageous conditions of cyclopropane carboxylic esters previously cited, including a chain dibromovinylic dichloro or_T- α-cyano alcohol 3-phenoxy optically active benzyl (e) OD construction, esters which have, exceptionally high insecticidal activity.

The 2.2-dimethyl 3r - (2.2 above dichlorovinyl) cyclopropane 1r-carboxylate (e) α-cyano 3 a-phénoxybenzyle and 2_F. 2 a-diméthyl3H (2.2 above dichlorovinyl) cyûlopropane-to-1r-carboxylate (R.) α-cyano 3 a-phénoxybenzyle are not described in the literature.

' These compounds are part of the invention.

The first case compounds, it is to say the alcohol ester

(E), is particularly suitable for 1' application to the control of insects in agriculture.

For example, it makes it possible to effectively against aphids, the cabbage, Coleoptera. It may also be used as an insecticide in the domestic (flies, mosquitoes).

Tests, given in the experimental part, demonstrate the insecticidal activity cleaved thereof against housefly and Spodoptera Littoralis larvae on.

The 2.2-dimethyl 3k - (2.2 above dichlorovinyl) cyclopropane 1r-carboxylate (R.) α-cyano 3-phenoxy benzyl is capable of insecticidal activity less intensity than the alcohol ester (e) correspond.

The invention also relates to the insecticidal compositions containing, as active principle, the 2.2-dimethyl dy (2 ^ 2 a-dichlorCvinyl) cyclopropane 1r-carboxylate (e) α-cyano 3-phenoxy benzyl and those that contain, as active principle, the 2.2-dimethyl 3r - (2.2 above dichlorovinyl) cyclopropane-IR-carboxylate (R.) α-cyano 3-phenoxy benzyl.

In these compositions, the active ingredient may be added -? offspring essentially of 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 stored characteristics/or a surfactant, nonionic, providing, further, a uniform dispersion of substances that make up the mixture. The vehicle can be a liquid, such as water,, alcohol, hydrocarbons or other organic solvents, mineral oil, animal or vegetable, a powder, such as talc, clays, silicates ^ kieselguhr or a solid fuel, such as tabu powder (or grounds pyrethrum).

To enhance the insecticidal activity of the two compounds mentioned above, it is possible to sum them up with synergists employed conventional in such a case, such as the I * - (2, 5, 8 a-trioxa dodecyl 2 propyl 4.5 to-methylenedioxy) benzene (or piperonyl butoxide), n - (2 a-éthylheptyl)/2, 2, 1 - bicyclo-/ 5-heptene-to-2.3-to-dicarboxiniide, the piperonyl-bis 2 - (2¹ - n-butoxy ethoxy) ethyl aces floor in (or tropital).

These insecticidal compositions contain, preferably, between 10 and 0,005% % by weight of active material.

The following examples illustrate the invention without limiting same *

Example 1 : Transformation of 2.2 to-dlnétdlnét.hyl 3R - (2. , ' 2 a-dibroinov3nyl;

the cyclopropane - the-carboxylate-cyncyn.no (R.) p Phénoxybcnzyle in 2.2-dimethyl 3r - (2.2 to-âlbromovinyl) cyclonropane-a 1 R-carboxylate ' (e) of CX a cyano ' a j-nhénoxybensyle.

5 In 2, 5 - cm3, d '1 g of isopropyl alcohol is introduced 2.2-to-diEéthyl' 3r (2.2 to-dlbromovinyl) - cyclopropane-IR-carboxylate (R.) α-cyano 3 a-phénoxybenzyle ' ^ l - 30.5 degrees/has/(=1 - O-benzene) or α ^=// - 25, 5⁰ (c=1 chloroform), and then aqueous ammonia solution of 0.15 cm3 22° Be, stirred for eighteen hours at 20 °c, isolates, 10 by dewatering the precipitate formed, washed, dried and obtains

•0.9 g of 2.2-dimethyl 3r (2.2 to-dibromovinyl) - cyclopropane 1r-carboxylate (e) α-cyano•3 '% iïénoxybenzyle, r=100 °c, // O ^=+ 60.5 degrees (c=1 benzene)/d/j ^~=+ 25 degrees (c=1 %, chloroform).

Analysis^C 22^H 19 °3 ^^{the R} 2 C. 502.2)

15

Calculated

H Ε lo Brr $

52.3 3.79 ' 2.77 31.63

Found 52.2 4.0 2.7 31.5

Example 2 : Transformation of 2.2 to-Aiméthyl 5r - (2.2 to-dibromov; -, lamdavl) the cyclopropane; 1 - R-carboxy the Te (the R) α-cyano 3 a-Phénoxybenzyle

20 in 2.2 above diraéthvl 3r - (2 a-.2 a-dibromcrvinyl)

i cyclopropane 1r-to-carboxylat(e) of α-cyano 3 a-Phénoxybenzyle.

At the start of 1 g of alcohol ester (R.), by operating in a manner similar to that of 1 ** example 1 but using 0.30 cm3 of an aqueous ammonia solution to 22° Be, obtained 0.9 g ester 25 D.¹ (e) alcohol of the same quality as the example 1.

• Example 3 : Transformation of 2.2-dimethyl•dy - (2.2 to-dibromovinvl) cyclopropane 1 the R-carboxylate (R.) α-cyano 3 a-phénoxybenzyle in 2.2-dimethyl - 3r(2.2-to-dibromovinyl) cyclooropane-th-carboxylate (e) of α-cyano 3 a-phénoxybenzyle/

.3' 0 Au. starting 1 g ester alcohol (fii), using a procedure similar to that of the example 1 but by replacing ammonia by 0.16 g of triethylamine, obtained 0.87 grams

¹ alcohol ester (e) of the same quality as the example 1.

Example 4' : Transformation of 2.2-dimethyl 5r - (1 - 2.2 ά bromovi ην, 11 55 ; - cyclopropane 1r carboxy] ,ate of (the R)-cvano 3-to-a-nbénoxybenzylein ' 2, . 2 d-3r methyl 3 - (2.2 to-dibromovinyl) cyclopropane 1 R because boxy ETL (8) of. q evano 5 a-pbénoxybenzyle.

At the start of 1 g of alcohol ester (R.), using a node operation similar to that of the example 1 but by replacing ammonia by 0.32 g of triethylamine, 0.9 g of obtained alcohol ester (e) of the same quality as the example 1.

5 Jixemnüe : Transformation of 2.2-dimethyl 5r - (2.2 to-dibromovlnyl1 cyclopropane 1r-to-carboxyiate of (the R) O cynno 3 a-Phénoxybenzyle in 2.2 above diméthvl ' 3r - - (- 2.2 to-dihromovinvl) cyclooropane IR-carbcxylate(e) of the cyano - 5 a-ohénoxybenzyle&.

At the start of 1 g of alcohol ester (R.), using a procedure similar to that of the example 1 but by replacing ammonia by 0.11 g of pyrrolidine derivatives, 0.80 g of obtained alcohol ester (e) of the same quality as the example 1.

6 Rxemnle : Transformation of 2.2 to-dinéthyl 3r - (2.2 to-dibromoyinyl) cyclopropane 1 the R-carboxylate (R.)-cyano 5 a-~Phénoxybenzyle in 2.2 above difséthyl 5r - (2" 2 a-dibromovinyl) cyclopropane 1 R-carboxylate of (if n evano5 ->Phénoxybenzyle.

At the start of 1 g of alcohol ester (R.), using a procedure similar to that of the example 1, but replacing the ammonia by 0.13 g of morpholine and by stirring for ninety-six hours at 20 °c, 0.9 g of obtained alcohol ester (e) the same quality as in example 1 to 11.

Example 7 : Transformation of 2.2 to-diméthvl 3r -(2.2-to-dibrômoviny1) cyclopropane 1 R because the boxy/L-T-W /|) α-cyano-a j-phénoxybencyleerï 2.2-to-diroéthyl Η 5 - (2 ^ 2 ^ - ά îbromovinyl) cyclopropane 1 R-carboxylate (e) of α-cyano 3 a-phénoxybenzyle.

At the start of 1 g of alcohol ester (R.), using a procedure similar to that of the example 1 but by replacing ammonia by 0,008 g of soda, 0.85 g of obtained alcohol ester (e) of the same quality as the example 1.

8 Kxomnîo:

Transformation of 2.2 to-dIraόthy1 3r - (2

2 a-dibroiii ·· ν C. ny is the j). )cyc, 1 οpropane-to-1r-ACΐ1 · boxy ATs ℮ OD (R.)-ryano ' a j-phdnoxybenzyl ο-c-n-2.2 D-I-Η 2methyl - 3 (-2, 2 a-dibromovinyl) cyclopropane 1r-to-carboxy1ητ ℮ of (3) the O-cyano-2 n] icnoxyben2yle.

At the start of 1 g of alcohol ester (R.), working in an analogous manner to that of the example 1 but by replacing the 2.5 cm3 isopropanol by 2.5 cm3 of butanol, obtained 0.80'g alcohol ester (e) of the same quality as the example, 1.

Example 9 : Conversion of the 2, 2-dimethyl 3r - (2.2 to-dibromovinyl) cyclooropacyclooropa.ne and 1 R ôarboxvlate of α-cyano (R.) 5 a-phénoxybenzyls in 2.2-dimethyl; R.>(2.2 to-dibromovinyl) - cyclopropane 1 R-carboxylate (e) of the Q-cyano-5 a-phenoxybenzyle.•

At the start of 1 g of alcohol ester (R.), working in an analogous manner to that of the example I-, but by replacing the 2.5 cm3 isopropanol by 2.5 cm5 of terbutanol are, 0.85 g of obtained alcohol ester (e) of the same quality as the example 1"

10 jâxemple : Transformation of 2.2 to-diaéthdiaéth.vl 3R - (2.2 to-dibromcyinyl) cyclopropane-RT carboxvlate (R.) of α-cyano 5 a-phénoxybengyle in 22 a-dlméthyl. 3R - (2,2 a-dibromovi lamdavl) cyclopropane IR-carboxylate (e) of the n-cyano-3 a-nhénoxybenzvle.

2 Cm3 mainly in a mixture of acetonitrile and water 0.5 cm3, is dissolved ester 1 g of¹ alcohol (R.), adds 0.15 cm3 of an aqueous ammonia solution 22° Be, stirred for eighteen hours at 2û^C. C., isolates by dewatering the precipitate formed, washed with acetonitrile to 25, 5" d'eau, at once dry and obtains 0.87 g of alcohol ester

(E) of the same quality as the example 1.

Example 11 : Transformation of 2.2-dimethyl 3r - (2.2 to-dibrocpdibrocp.ovinvl) cyclopropane 1r-carboxylate (R.) α-cyano 3 a-phénoxphénox.vbenzyle in 2.2 d-iraéthyl R. - 3 (2.2 to-dibromovinyl) cyclopropane 1 R because boxy ETL (e) of the R-cyano-3 a-phénoxybenzyle.

At the start of 1 g of alcohol ester (R.), using the same procedure as the example 9, using 2.5 cm3 of terbutanol are, but by replacing ammonia by 0.16 g of triethylamine, 0.8 g of obtained alcohol ester (e) of the same quality as to 1' example 1.

Kxoronle 12 : Transformation of 2.2 to-diméthyl~diméthyl~3r -(2.2-to-dibromcvjnvl 1 cyclopropane 1it-to-caca.rbcxylate of (the R) α-cyano 3 a-phénoxybenzyle in

2, 2 d-j-INH 'VI' L-Jii~( 2, 2 dL bromov. I-lamdavl)

oD (YI) ΐ) - ρν··ΐηο 5 a-PHFs; n-I->: ybon2yIc.·

cyο1upropane-a 1!-<<

rbosv. - · ·;.

At the start of I g ester alcohol (K.)" using the in-$; OA procedure as in example 8 using 2, b. cm3 of butanol, but by replacing ammonia by 0.11 g of pyrrolidine derivatives, 0.8 g of obtained alcohol ester (e) of the same quality as the example 1. 1 j-O-üyüy.cmnl

Transformation of 2.2 to-dd.jméthyl 5R~(2, 2 a-dnbromovlr.

-,>

r onrboxylatecyclopromne and 1 of (the R, S) O-to-eyano 3 a-nhcnoxybenrr^F. in the 2.2-dimethyl 3r - (2.2 to-dlbromovjnyl) cyelopropane-to-1r carboxylate (3) a-cyacya.no 3 A-Phénoxybenzyle.

105 g of 2.2-dimethyl 3r - (2.2 to-dibromovinyl) - cyclopropane group; Acarboxylate of (ll, e)/3~phénoxybenzyle / α-cyano-^=0° -1 to^I (=C. 1ÿi, chloroform), and TDC=// ^ + 14 degrees (je=1 benzene) are 262.5 cm3 dissolved in isopropanol. To the solution is added

15 cm3 of an aqueous ammonia solution to 22° Be, stirred for

eighteen hours at 20 °c, isolates by dewatering the precipitate formed,

UVDi ' /!

the isopropanol 103 cm3/washed, dried, and obtains 95.1 g of

2.2-dimethyl 3r - (2,2 a-dibromovinyl) cyclopropane 1 R oarboxylaue

20

(e) the bo j-U-cyano ->phénoxybenzyle. The j?=100 °0, α=// ^ + 60,

(c=1 benzene) of the same quality as the example 1.

Example 14 : Transformed the j is the ' 5r 2.2-dimethyl - (2.2 d-j-bromovl rr.vl 1cyclonrooanë-to-1r-to-oarboxylate of (the R, O) O a cyano 3 a-rhénoxybenzyle in 2.2-dimethyl 3r - (2.2 to-dibromovlnyl) cyclonronane-to-LP-carboxylates (e) of the O-cyano-3 a-Phénoxybsnzÿle•

In 2.5 cm3 of isopropanol, 1 introduced g ester of racemic alcohol (the R, O), added 0.30 cm3 of an aqueous ammonia solution to 22° Be, stirred for twenty hours to 20 °0, isolates by dewatering the precipitate formed, washed by 1 cm3 D.¹ isopropyl alcohol, dried and obtains 0.9 g ester alcohol (3) of the same quality as the example 1.

Example 15 : Transformation of 2.2-dimethyl 3r - (2.2 to-dibromovinvl) cyclopropane 1r-carboxylate (R._{the R} 3) the O-cyano-3 a-Phénoxybenzyle in 2.2-dimethyl 3r - (2.2 to-dlbromovjnyl) r carbcxvlatecvclopronane and 1 (e) of the O-a-cvano 3 a-Phénoxybenzyle.

In 2.5 cm3 of isopropanol, 1 introduced g ester of racemic alcohol (the R, O), 0.16 grams of triethylamine is added, stirred for fifteen hours at 20 °c, insulated. dewatering the precipitate formed,

1 ο 1 cm3 washed with isopropanol, the dry and obtains ϋ, υ / alcohol ester (e), of the same quality as the example 1..

hxemnhxemn.lo 16 : Transformation of 2.2 to-dlmf-to-thyI 3r - (2.2 to-dlorori■virvir.vl;

dEYE] opropnnc IR-oarboxylate of (the R, 3)" a cyano - 3 a-phénoxyben Vl grams

5 in 2.2-dimethyl 3r - (2.2 to-dihromovlnyI) cyclopropane 1r-to-earb

(e) of " a cyano - 3 a-Phcnoxybenzyle.

In 2.5 cm3 of isopropanol, 1 introduced g ester of racemic alcohol (the R, O), adds 0.32. g of triethylamine, stirred for fifteen hours at 20 °c, isolates by dewatering 3b precipitate formed, the

washed with isopropanol 1 cm3 ΐ σ, the dry and obtains 0.9 g of alcohol ester (e), of the same quality as the example 1.

17 jyxomple : Transformation of 2.2 to-dinéthyl 3r~(2, ~dibromcvinvi .2) the cyclopropane IR-carboxvlate of (the R, O) O-cyano-5 a-Phénoxyben: ' yl 2_{the R} 2-dimethyl. 3R - (2 -._T- 2 a-dfbromovinyl) cyclopropane 1 R-carboxylate 15 (e) of 3 a-phénoxybenzyle-cvano.

In 2.3 cm3 of isopropanol, 1 - introduced alcoci g ester of racemic (the R, O), 0.13 g of morpholine is added, stirred for four twenty-sixteen hours to 20 °0, isolates by dewatering the precipitate formed, washed by 1 cm3 of isopropanol, the dry and obtains 0.9 g ester 20 (e) alcohol of the same quality as the example 1.

18 DxemPle : Transformation of 2.2 to-diméthvl 3r - (2.2 to-dihrordihror.ovinvl) cyclopropane 1r-carboxylate (R s) of Q-cyano-5 a-nhnh.énoxybenzvls in 2.2 above diméthvl 3r - (2.2 to-dibroisoyinyl) cyclonropane-IR-carboxylate of (E) dC-cyano-3 a-phénoxybenzyle.

the m In 2.5 cm3 of isopropanol, 1 g of introduced 2.2-dimethyl 3r (2.2 to-dibromovinyl) - cyclopropane 1r-carboxylate (the R, 3) α-cyano 3 a-phénoxybenzyle, adds 0,008 g of soda, stirred for eighteen hours at 20 °c, isolates by dewatering the precipitate formed, washed by 1 cm3 of isopropanol, the dry and obtains 0.85 g ester $0 (e) alcohol of the same quality as the example 1.

hr ' example 19 : Transformation of 2.2 to-diméthvl 5r - (2.2 to-dibromovinyl) the R-carboxy-cyclopropane 1 ETL of (the R, O) O-cyano-3 a-phénoxybenzyle in 2.2-dimethyl 5r (2.2 to-dibromovinyl) - cyclonronane-to-LP-carboxvlats(e) of α-cyano 5 a-nhénoxybenzvle.

1 G of dissolving racemic alcohol ester (the R, O) in a mixture of 2 cm3 acetonitrile and 0.5 cm3 of water, added 0.15 cm3 of an aqueous ammonia solution to 22° die, stirred for seventeen hours at 20 °c, isolates by dewatering the precipitate formed,

washed with due 1' acetonitrile derivative to 25 % water, dried, and, obtains 0.87 grams of ester-to-of alcohol (e), of the same quality as the example 1.

one introduced 10 g of 2.2-dimethyl 5r - (2.2 to-dibromovinyl) - cyclopropane group 1 the R-carboxylate (O, O) α-cyano 3 a-phénoxybenzyle / α=^ / ·· 0 degrees, -1 degrees (theS SSs 1 TD, chloroform) and / α / ^ 0=+ 140 (c=1 benzene) in isopropanol 20 cm3, stirred for eighteen hours at 2ü^& C., isolates by dewatering the precipitate formed, washed with isopropanol 10 cm3, the dry and obtains 4 g ester alcohol {S}. W ≈ 100 °c, 4 - 60 degrees (c=1/i, benzene).

One joins the filtrate and wash liquors and obtains a solution (solution L.) which contains 5 g of 2.2-dimethyl 3r (2.2 to-dibromovinyî) cyclopropane 1 the R-carboxylate (R.) α-cyano 3 a-Ph.D." c3Eybenzyls and 1 g of 2.2-dimethyl 3r (2.2 to-dibromovinyl) - cyclopropane 1r-carboxylate (e) α-cyano 3 a-phénoxybenzyle.

fe) reaction of the mixture of alcohol ester and ester (R.) (e) alcohol ester in'd ' alcohol (if):

Has the solution 1, added 0.8 cm3 * concerns aqueous solution of ammonia to 22° re, stirred for twenty hours at 20 °c, isolates, by dewatering strip precipitate formed, washed with isopropanol 5 cm3, dry and obtltnt 1s 4" 5 g of 2.2-dimethyl 3r (2.2 to-dibromovinyl) - cyclopropane 1r-carboxylate (e) α-cyano 3 a-phénoxybenzyle.

The I *=100®C., α ^ ss + 60 degrees //(c=1 with fo_T- benzene) of the same quality as

Biliary cirrhosis enrol E 21 : transformation of 2.2-dimethyl 3r - (2.2 and the DJ toto chlorovir VLs ^.cyclopronane-to-1r-carboxylate (R.) 3 a-phénoxybenzyle-cyaho

in 2.2-dimethyl 5r - (2.2 to-dichlorôvinyl) cyclopropane 1r carboxylate (e) of Q cc.vano 3^phénoxybenzyle.

a) preparation of the alcohol ester of structure (the R):

10 grams of d¹ racemic alcohol ester (the R, O), of/has / ^^Û =+ 16.5 DEGREES

The c ^=9.ï|&beiizèhe) chromatographies are OsUâht silica gel with a mixture of petroleum ether (Ilb. 40° - 70 °c) and " isopropyl ether {85/15), 5 grams OD obtained 2.2-to-diméthyi 5 K. (2.2 above dichlorovinyl) cyclopropane-IR-carboxylate (the R) U-cyano 3^phénoxybenzylc'd */ / α ^⁰ =-31 degrees (c=i cents, benzole) or // has²⁰ -21=, -. (c=1/i, chloroform).

b.) ART nsec F. raining in eater D.¹ (e) alcohol of structure :

60 G of 2 ^-substituted dimethyl - 3r - (2.2 above dichlorovinyl) cyclopropane-to-1r-carboxylate (R.) 3 a-phénoxybenzyle-eyaho=// has -31 degrees (c=1 - Js is, benzene) or α=// ^ " 21.5 degrees ($c=1, chloroform) obtained at 20, 1) - 2o

paragraph has), is amodie 120 cm3 D.¹ isopropyl alcohol and then 9 cm3 of aqueous solution D.¹ skudlik ^ EUF to 22° Be, cooled to 0 °c, stirred for forty-eight hours to? 0 °C, isolates by dewatering the precipitate formed, washed with 50 cm3 D.¹ isopropanol at -20 °c, the dry and ob -

holds 46.5 g of an ethyl - 2.2^d'ii&3r (2.2 above dichlorovinyl) cyclopropane 1?. - carboxylate (e) α-cyano 3 a-phénoxybenzy1e. F.=60 °c ., // α=20° to + 66 * ^

(c., =1%, benzene) or=+ 34 degrees (c=1 DEGREES/<>, chloroform).

Example 22 : Transformation of 2.2-dimethyl 3r - (2.2 to-dichIorovinvl) cyclopropane 1 - carboxyla R-T-e of (the R, O) O-to-cyono 3 a-nhénoxybsnzyIe in 2.2 above diméthvl 3r - (2" 2 a-dichlorovinyl) cyclonropane-to-LP-carboxylates (e) of the TX-evano 3 a-Phénoxybenzvie.

With 600 g of racemic alcohol ester (the R, O), ^=// α + 16.5 degrees (c=10 benzene), 1200 cm3'd * isopropyl alcohol is added, and then introduced into the resulting solution, 90 cm3 of an aqueous ammonia solution to 22®Be, cooled to 0 °c, stirred for forty-toto huir hours at this temperature, the resulting precipitate is isolated by dewatering, washed with isopropanol to -20 °c 300 cm3, the dry and obtains 485 g of 2.2-dimethyl 3r - (2.2 above dichlorovinyl) cyclopropane 1rcar boxy ETL (e) of α-cyano 3-phenoxy-benzyl E f=60®C., ο./ / _2Q=+ 66 degrees (c-Ra of 1 j-&, benzene) or α=// ^ + 34 degrees (c=1 the j ", ^ chloroform).

Example 23 : Transforming the 3r 2.2-dimethyl - (2¹_{the R}2¹dibromovinyl, çydloPropane-to-LP-carboxylate (R._F. E) a cyano 3 ^ pphSnoxybenzyle in 2.2-dimethyl 3r - (2¹ , 2' dibromovinyl) cyclopropane LP-carboxylate (e).

" d-α-cyano 3 a-phénoxybenphénoxyben.zy the.

! 10 G of dissolved 3r 2.2-dimethyl - (2 ', 2' a-dibromovinyl) - cyclopropane-LP-carboxylates^; of (the R, e) a cyano - 3 a-phénoxybenzyle ^, (^) ^ ≈ 0° to - 1° (c=1%. -, chloroform) and (^) ^ Ρ 14° +=(c - 1 c/o, benzene) in 25 cm D.¹ the isopropanol, added 0.8 g of dnsopropylamine, stirred for 6 hours at 2O °C then: 2 hours at 0 °c, isolates by squeezing the

the I

precipitate formed, the crystallizes in 2 volumes of isopropanol and

obtains 8.04 g of 2.2-dimethyl 3r - (2 ', 2' a-dibromovinyl) cyclopropane Ir carboxylate £e) a cyano - 3 a-phénoxybenzyle (OQs ^=+ 57°

' (c=4%, toluene)*

Example : Transformation of 2.2 to-diméthy 3r 1 - (2', 2¹ - dibrc mo -Vinyl) cyciopropane-to-LP-carboxylate cÿano 3 a-phénoxybenzvle in 2.2-dimethyl 3r - (2 ', 2' dibromovinyl) cyclopropane LP-carboxylate (e) a cyano - 3 * ^ - 3 a-phénoxybenzyle.

Operations are carried out in process like the example 23, but under stirring for 48 hours at 0 °c, and obtains the same product yield of the same quality as the example 23.

Example 25 : Transforming the 3r 2.2-dimethyl - (2 ', 2' a-bromovinyl) cyclopropane LP-carboxyl of ETL (the R, O)_ o4-to-dÿano 3 a-phénoxybenzyle in. 2.2-to-diméthy1 3r - (2 ', 2'■dibromovlnyl) cyclopropane LP-carboxylate (e)

' a cyano 3 a-phénoxybenzyle.

the I

; Operations are carried out in process like the example 23, but in

T-

replaced 1 'isopropyl alcohol by 1' isopropanol at 3.5% water, in waving - 8 during tiOtires 'to 20®C., and obtained 8.16 g of 2.2 to-àiràir.éthy 1' 3r - {2',2 * - dibrôm0<? confectioneries "-yl) cyclopropane LP-carboxy-Te of the cyano group (e) 3 a-phénôxÿbenzÿlê 1 ml)=+ Q-® 5, 6.5 degrees (c=4%, toluene).

Example 26 : Transforming the 3r 2.2-dimethyl - (2¹ , 2' - dlbrono -

Vinyl) cyclopropane LP-carboxylate (the R, 5) 4 - ο

the I in one cyano 3 a-phénoxybenzyle 3r 2.2-dimethyl - (2 ', 2'! ', dibromovinyl) cyclooropane-to-LP-carboxylate (e) Y a cyano - 3 a-phénoxybenzyle ^.

The I is dissolved 10 grams>3r of 2.2-dimethyl - (2 ', 2' a-dibromovinyl) - cyclopropane-LP-carhoxÿlate of (the R, O) of OC a cyano - 3 a-phénoxybenzyle=

0|^I to - ii * (c=1%, chloroform) et=+ 14 degrees (≈ 1% C., benzene) U-3!

. 25 cm in isopropanol, added 1.39 g of pipëridine, stirred for 18 hours e 28 * 0, isolates by dewatering the precipitate formed, the 'novel layout © to 1' isopropâriol, dried and obtains 8.6 g of 2.2-dimethyl 3r; {2 */ 9.ï ' a-dibromoyiïïfîlj cyclopropane LP-carboxylate (e) a cyano - I ^ ^ 3 a-phéîî4; henzyie identical to the product obtained in the examples 23 to 25 *.■

Example 27 ; Transforming the 3r 2.2-dimethyl - (2¹ , 2¹ - dlbrcraovinyl) cyclopropane LP-carboxylate (the R, e) the L-cyano-O-<3 a-phénoxybenzyle in 2.2 above àiméthyl ' 3r - (2¹ , 2¹dibromovinyI) cyclopropane LP-carboxylate (e)

5 a cyano-OC^3 a-phénoxybenzyle.

façdn operations are carried out analogous to example 26, but by replacing the 1.39 g of piperidine by 1.66 g of isopropylamine, and obtains initially of 10 g ester alcohol (the R, O), 8.85 g ester ' alcohol (e) of the same quality as the examples 23 to 26.

1.0 Example 28 ii Transforming the 3r 2.2-dimethyl - (2', 2¹ - p-dibrorr.yinvllt cyclopropane LP-carboxylate (the R, e) a cyano 3 a-phénoxybenzyle in 2,2-dimethyl 3r - (2¹ , 2' dibromovinyl) cyclopropane Ir carboxylate ά℮ (O?

a cyano - 3 a-phénoxybenzyle.

15 Operations are carried out in process like 1' example 26, but by replacing the 1.3# pipér g of 2.7 g of ephedrine IDINEs by, under stirring for 24 hours 20 °c confectioneries, and obtained starting with 10 g of alcohol ester (the R, #), 8.7 g of alcohol ester (e), same quality as in examples 23 to 2?? -.

IÈÔ^!Example 29 9.ï Transformation of 2.2 to-diraëthyl 3r - (2 ', 2' a-dibrcnovinÿl) DEYE lopropane - LP-carboxyl of ETL (the R, O) ^T- GBP -> a cyano 3 a-phénoxybenzyle in 2.2 above dlméthyi 3r - (2 ', 2' ^ diirtovinyl) cyclopropane Ir carboxylate 5ë (e)

a cyano - 3 a-phénoxybenzyle.

25 Operations are carried out in process like the example 23, but by replacing the ' 0, 8 - g of diisopropylamine by 4.4 g of triethylenediamine (or D.A.B.C.O.), is obtained, after 72 hours stirring, to 20 °c, 7.5 g of alcohol ester (e) of the same quality as those obtained!

examples 23 to 28 jaux.

3 © J. Example 30'•Transforming the 3r 2.2-dimethyl - (2¹ , 2' - bromovinyl) cyclopropane LP-carboxylate (R._F. E) in one cyano 3 a-phénoxybenzyle 3r 2.2-dimethyl - (2 ', 2'dibromovinyl) cyclopropane LP-carboxylate (e)

a cyano - 3 a-ohênoxybenzyle.

'^{1, 1} "' *~^{: -} 3

£ôh said 10 g ester alcohol (the R, O) in 25 cm of isopro -

0.23 gpde potassium terbutylate added, stirred for

. [2ô l8 has!^rF C., and 7.7 g of obtained alcohol ester (e) of same^% |

•quality that examples 23 to 29. : -

Example 51 : Transforming the 3r 2.2-dimethyl - (2^,/ 2' a-dibromcvinyl). the cyclopropane IR-oarboxylato key (the R, O)^{the R} ><! in one cyano 3 a-phénoxybenzyle 3r 2.2-dimethyl - (2', 2¹dibromovinyl) cyclopropane LP-carboxylate (e)

Y a cyano - 3 a-phénoxybenzyle.

Operations are carried out in process like the example 50 by replacing the 0.23 g of potassium terbutylate by 0.34 g of isopropy 'ETL sodium, by stirring for 24 hours, to 20 °c, obtained' 7.3 g of alcohol ester PK) the same quality as in examples 25 to -

-50.

Example 52 : The 3r Transformâtion 2.2-dimethyl - (2¹ , 2' a-dibronoyinyl) cyclooropane-to-LP-carboxylate (the R, e) a cyano 3 a-phénoxybenzyle in 2.2-dimethyl - 3r<2¹ , 2' dlbromovinyl) cyclopropane LP-carboxylate (e) a cyano - 3 a-phénoxybenzyle ^.

Is dissolved lu g of 2.2-dimethyl 3r~(2 ', 2' - dibromovinyl) cyclopropane LP-carboxylate (the R, O)" ^ L-α-cyano 3 a-phénoxybenzyle

0° to - 1° (≈ 1% C., chloroform) and (^ 4)=+ ^ 14° (≈ 1% C., benzene) in 25 cm of isopropanol confectioneries 3.5 L of water, added 0.84 g of benzyl amine, stirred for 23 hours, to 20 °c, the precipitate obtained by dewatering isolates, the crystallizes in 2 volumes of isopropanol and obtains 8.25 g of 2.2-dimethyl 3r - (2 ', 2' a-dibromovinyl) cyclopropane LP-because boxy ETL of {O) C. #4. for cyano - (RO) 3 a-phénoxybenzyle ^ w=+ 57° (c=4%, toluene).

Example 53 ii Transforming the 3r 2.2-dimethyl - (2', 2¹ - bromovinyl) cyclopropane LP-carboxylate (the R, 5) 3 a-phénoxybenzyleoCçyano in 2.2-dimethyl 3r - c2 ', 2' - dibrornovinv3) cyclopropane LP-carboxylate (e) ^ a cyano - 3 a-phcnoxybenzyle.

10 G ester is dissolved alcohol (the R, O) in 25 cm³ isopropanol, added 1.20 grams, n-butylamine, stirred for 24 hours, to 20 °c, isolates by dewatering the precipitate formed, washed and dried, and

9.0 G of•obtains alcohol ester (e) of the same quality as the examples 25 to 52.

Example 54 ii Transforming the 3r 2.2-dimethyl - (2¹ , 2¹ - dibromovinyl) cyclopropane LP-carboxylate (the R, O) - O-< in one cyano 3 a-phénoxybenzyle 3r 2.2-dimethyl - (2 ', 2' dibromovinyl) cyclopropane LP-carboxylate (e)

• pc a cyano - 3 a-phérioxybenzyle.

By operating in a manner similar to that of 1 * exemple 32, but using 1.20 g of dry-butyl amine (1 methyl-propylamine hydrochloride or), under stirring for 24 he-to-close, to 20^0, 9.1 grams of d * is obtained alcohol ester (e) of the same quality as the natural * examples 23 to 33•

Example 33 : Transforming the 3r 2.2-dimethyl - (2¹ , 2¹ - dibronovinyl) cyclopropane 1 R carhoxylate of (the R, O)^F. in a cyano - 3~phéfloxybenzyle><2.2 a-substituted dimethyl 3r - (2 ', 2' -

•dlfapomovinyl) cyclopropane IR-carboxylate (O) this c. rpyano^3~phénoxybenzyle.

By operating of analogous to that of the example 30, but

3 replacing the 0.23 grams potassium terbutylate die by 0.64 cm - 40% aqueous solution of " tetra-butyl ammonium hydroxide, is obtained, after 24 hr&ûfèeë stirring, to 20 °c, 8.4 g of ester¹ (e) alcohol of the same quality as the natural * examples 23 to 34 -.

Example 36 : Transformation of 2.2 to-dlméthyl 3r - (2', 2¹ - dibrcmovlnyi) cyclopropane LP-carboxylate (the R, O)=a j-phënpxybenzyle<_cyano in 2.2 above diraéthyl 3r - (2', 2¹ ^ moyinyl emir) cyclopropane LP-carboxylate (e) c.. ^ yçyano3rpbénoxybenzy the.

i-dtSSput ii # ^ ^ * $|ester-alcohol (the R, O) in 25 cm³ of isopropamole, 10 adds gvdè AMBERLITE dioleyldimethyl 400 (a mesh size 20/50;

t-<&çud&yfctëreCOpâ is a styrene-divinyl benzene strongly

•basiqhô and quaternary ammonium functions), prêalablement. * x-washed with perchloric acid diluted at 1/3, confectioneries and water until neutral, then if 3a to soda water, stirred for 24 hours, to 20 * 0, isolated by Csaorngê - the precipitate (mixture of resin and alcohol ester (e), added methylene chloride, stirred, filter, concentrate the filtrate A. 7.8 g of dry and obtains alcohol ester (e) of ATP-ïtfême merit than ^ iéeêpies 23 to 35. - -

Example 37 THE T "Transformation of 2.2 to-substituted dimethyl - 3r (2¹ , 2¹ - dibrcmovipyi) "the cyclopropane - IR because boxy t e of (the R, O) P->^ CVano 3.-to-phénoxvbenzyle in 2.2-dimethyl 3r - (2 ', 2' dibromovinyl) cyclopropane LP-carboxylàte of (e)">4 - " 3 a-ohénoxybenzyleeyano.

Operations are carried out in ways analogous to that described in example 36 die, but using 1# g of AMBERLITE ir45 (20/50 a mesh size;

which is a copolymer e of styrene and divinyl benzene weakly basic ïtâs having primary amine groups, secondary and tertisiréè).., and obtains, after 72 hours stirring, to 20 °c, 8.1 theS<3' alcohol ester (e) quality identical to the products obtained in examples 23 to 36 islands.

; Example 3& : Transformation of 2.2 to-substituted dimethyl - 3r (2¹ , 2¹ - dibronothe I vimyl) cyclopropane-IR-carboxylate (the R, O) - L-<degrees

a cyano - 3 in the zyphénoxyben 3r 2.2-dimethyl - (2 ', 2' -

, dibromovinyl) cyclopropane LP-carboxylate (e)- 3 a-phénoxybenzyle ^ a cyano.

Operations are carried out in process like the example 36, but using 10 g of resin DOWEX of Ag 1x8 (a mesh size 200/400; and which is a exchanger D.^{the R} strong base anion character whose active moiety is a benzyl ammonium-trimethylsilyl group, the product containing 8% divinyl benzene), and obtains, after 72 hours stirring, 20 °c confectioneries, 7 g ester alcohol (e) quality identical to cells involved products obtained in the examples 23 to 37 *

Example 39 : Transformation of 2.2 to-substituted dimethyl - 3r (2¹ , 2' - dibro-to-.oyinyl) cyclopropane LP-because Te of the boxy (the R, O) - Q-^ -

Y in one cyano 3 a-phénoxybenzyle 3r 2.2-dimethyl - (2', 2¹ ' dibromovinyl) cyclopropane LP-carboxylate (e)

¹a cyano - 3 a-phénoxybenzyle.

|operations are carried out in process like the example 36, but using 10 g of Amberlite liquid ATIA (amines that are high molecular weight company replication and Haas, viscosity 72 eps 25 °c), and after 72 heufdt stirring, obtains 8.9 g of alcohol ester (e) of same quality as products of examples 23 to 38r~

; Example " 0the TTTransforming the 3r 2.2-dimethyl - (2 ', 2' - dibrcrr.cVinyl) cyclopropane-IR-carboxylate (RTR)⁰ *¹ - -a cyano 3 a-pnénoxybenzyle in 2.2 a-substituted dimethyl - 3r (2¹ , 2'dibromovinyl) cvclopropane-to-LP-carboxylate (e) &C. a cyano - 3 a-phénoxvbenzyle.

! Operation proceeds similarly as that of the example 36" but using 3.75 g of Amberlite liquid la2, viscosity 18 ESP s at 25 °c) and after 18 hours' stirring, to 20 °c, obtains 8.1 g of alcohol ester (e) quality identical to that of the products obtained examples 23 to 39 *

Example 41 ii) Transforming the 3r 2.2-dimethyl - (2', 2¹ the O - dlbror.vinyl) eyclopropane-to-LP-carboxyjcarboxyj.ate of (the R, ~O) ^ akt. in one cyano 3 a-phénoxvbenzyle 3r 2.2-dimethyl - (2 ', 2' dibromovirty 1) cyclopropane IR-carboxy ETL (e) of ^ Degrees a cyano - 3 a-phénoxybenzyle.

i-is carried out die process like 1' exemple26, but by replacing 1 * 1 * isopropanol-isopropyl alcohol by 3.5 to % water, and obtains, by stirring for 24 hours, to 20 °0, 8.95 g of alcohol ester (e) of the same quality as that obtained examples 23 to 40.

Example 42 : Composition 2 thereof, 2-dimethyl 3r - - (2._T- 2 a-âichlorovinyl) Cy of clouropane-to-1r-to-earboxylate of (e) α-cyano 3-phenoxy Basi unreported pregnancy.

2.2-dimethyl 3r - - (2.2 to-dicblorovinyl) cyclopropane 1 the R-carboxylate (0) CD-cyano-benzyl 3 a-pbénoxy....... 25 g/l

2.6-to-diterbutylpsæsorésol - 10 g/l

- EHCOL 300 hr * b...... 50 g/l

EMCOL - 5 © 0 b * 20 g/l hr

** - Supersol .786 g/l * these surfactants are mixtures of active calcium salts of alkyl benzene sulfonates (anionic portion) and polyoxyethylene (part nonionic), marketed by the dealer/V-ite-. =

** The Supersol is a blend of aromatic solvents available from dealer P.O. Box * (interface shell).

Study of the insecticidal activity of the 2.2-dimethyl 3r - (2.2 above dichlorovinyl) - cycloprooane-to-1b>carboxyIate of α-cyano (e)3-phenoxy benzyl (Al compound.

Has - study of 1' ITAC ^ tLLs insecticidal against the fly - give

Insects teâtjs blow flies are of mixed sex. It is performed by topical application of 1 JHA of acetone solution on the thorkx back insects. 50 vidus standing upward trend is used per treatment. We monitor mortality twenty-four hours after treatment and determines the lethal dose 50 of the compound.

Experimental results obtained are summarized in the following table:

Dose■^C. the O / of mortali - 24 hr tee. ÎI50

5, .¹'ll 93.3

^ 0,625 hi and $ 1 * 25 ¾.■83.2 10.0 68.0 34.5 by insect 1.6 ' nano-gram

Concluding : The compound is capable of very high insecticidal activity against housefly.

B. - study of the insecticidal activity against larvae Littoralis Littoralis

The assays are performed by topical application. Depositing an acetone solution of product to be tested on dorsal thorax of each individual. NC utilizes Spodoptera Littoralis caterpillars * 15, at 4ème larval stage, for each dose employed.

After processing,: webs individuals. are placed on an artificial diet (Poitot medium). We monitor efficiency (percentage mortality taking into consideration a untreated control), 24 hours, 48 hours after treatment and then determined the dose spreads 50 (LD ^₀ ) in nanograms per track.

The experimental results are summarized in the following table: