CH637371A5 - ESTERS OF SUBSTITUTED ACETIC ACID AND SUBSTITUTED BENZYL ALCOHOL THEIR PREPARATION PROCESS AND THE INSECTICIDE COMPOSITIONS CONTAINING THEM. - Google Patents

Description

The present invention relates to esters of optically active substituted acetic acid and of racemic or optically active substituted benzyl alcohol, endowed with insecticidal properties, their process of preparation and the insecticidal compositions containing them.

A more specific subject of the invention is the esters of α-cyano 3-phenoxybenzylic alcohol and 2-isopropyl 2-parachlorophenylacetic acid, of general formula:

ch in which the acid residue is in the D or L form, has an asymmetric carbon of determined configuration, and in which the alcoholic residue has an asymmetric carbon of configuration (R), configuration (S) or racemic.

Among the compounds of the irivention, there will be mentioned more particularly:

alcohol ester (RS) a-cyano 3-phenoxybenzylic acid L

2-isopropyl 2-parachlorophenylacetic,

alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D

2-isopropyl 2-parachlorophenylacetic,

alcohol ester (S) a-cyano 3-phenoxybenzylic acid D

2-isopropyl 2-parachlorophenylacetic,

the alcohol ester (S) a-cyano 3-phenoxybenzylic acid L 2-isopropyl 2-parachlorophenylacetic acid.

A subject of the invention is thus the esters of general formula (I), and more particularly those which are named above, perfectly defined as regards their steric configuration.

The invention particularly relates to:

- the alcohol ester (RS) a-cyano 3-phenoxybenzylic acid L 2-isopropyl 2-parachlorophenylacetic acid, steric configuration determined and an = + 6.1 ° (c = 1% in the ethanol),

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- the alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic, of steric configuration determined and a ^ = - 5 ° (c = 1.2% in l 'ethanol),

- the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid, and in particular the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic in the pure state, crystallized, melting point 62 ° C and a ^ 0 = + 13.15 ° (c = 2% in benzene).

The subject of the invention is also a process for preparing the esters of general formula (I), characterized in that the DL 2-isopropyl 2-parachlorophenylacetic acid is reacted either with (+) a-phenylethylamine to obtain , after crystallization from a mixture of water and ethanol, the (+) a-phenylethylamine salt of L 2-isopropyl 2-parachlorophenylacetic acid, or with (-) a-phenylethylamine to obtain, after crystallization from a mixture of water and ethanol, the salt of (-) a-phenylethylamine of D 2-isopropyl 2-parachlorophenylacetic acid, acts on the salt obtained an acid, in the presence of water, to obtain the L 2-isopropyl 2-parachlorophenylacetic acid or D 2-isopropyl 2-parachlorophenylacetic acid and reacts one of these optically active acids, or a functional derivative of this acid, with α-cyano 3-phenoxybenzyl alcohol configuration (R), configuration (S) or configuration (RS), or with a metal or halogenated derivative of this alk ool.

The crystallization of the α-phenylethylamine salts of D or L 2-isopropyl 2-parachlorophenylacetic acids can advantageously be carried out in ethanol at 70% water (by volume).

The splitting according to the method of the invention of DL 2-isopropyl 2-parachlorophenylacetic acid using a-phenylethylamine provides, for the first time, and with good yield, the acids D and L 2-isopropyl 2-parachlorophenylacetics.

The subsequent esterification with racemic or optically active α-cyano-3-phenoxybenzyl alcohol can be carried out conveniently using the chloride of these acids D or L, preferably by operating in the presence of a tertiary base such as pyridine or triethylamine and within an organic solvent such as benzene, toluene, or methylene chloride.

This esterification can also advantageously be carried out using anhydride or mixed anhydrides of D or L 2-isopropyl 2-parachlorophenylacetic acids.

To obtain the esters (I), it is also possible to react a chloride of D or L 2-isopropyl 2-parachlorophenylacetic acid with a metallic derivative of α-cyano 3-phenoxybenzyl alcohol, such as an alkali metal derivative. .

It is also possible, to obtain the esters (I), to react a halogenated derivative of the alcohol with an alkaline salt of the acid.

The chlorides of acids D and L 2-isopropyl 2-parachlorophenylacetics are conveniently obtained by the action of thionyl chloride on the corresponding acids. The other functional derivatives of these acids, as well as the functional derivatives of α-cyano 3-phenoxybenzyl alcohol, can be obtained by known chemical means.

A more particular subject of the invention is a process for preparing the alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid, characterized in that the reaction l D-2-isopropyl 2-parachlorophenylacetic acid with thionyl chloride, within benzene, and subjects the chloride of D 2-isopropyl 2-parachlorophenylacetic acid to the action of alcohol (R, S) a -cyano 3-phenoxybenzylic acid, within benzene, in the presence of pyridine, as well as a process for the preparation of the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid , characterized in that the 2-isopropyl 2-parachlorophenylacetic acid is reacted with thionyl chloride, within benzene, and the resulting D 2-isopropyl 2-parachlorophenylacetic acid chloride is subjected to the action alcohol (S) a-cyano 3-phenoxybenzyl, within benzene, in the presence of pyridine.

A subject of the invention is also a process for preparing the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-iso-propyl 2-parachlorophenylacetic acid, characterized in that the alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic to the action of a basic agent in a solvent or a mixture of solvents in which l alcohol ester (S) is insoluble. As basic agent in this epimerization, it is advantageous to use ammonia and, as solvent, isopropanol.

In fact, in Example 4, given in the experimental part, using a suitable solvent such as isopropanol, in which the alcohol ester (S) a-cyano 3-phenoxybenzyl is poorly soluble, it is possible, by adding a crystallized alcohol ester (S) a-cyano 3-phen-oxybenzyl ester primer to the alcohol ester (RS) a-cyano 3-phenoxybenzyl ester solution, obtaining, after a sufficient time, by insolubilization, a first fraction of alcohol ester (S) a-cyano 3-phenoxybenzylic acid D. The subsequent concentration of the mother liquors provides a residue consisting of a mixture of alcohol ester (R) and alcohol ester (S) rich in alcohol ester (R), the mixture being subjected to the action of a base, in an insolubilizing solvent, the alcohol ester (R) first tends to give a racemic mixture of alcohol ester (RS). However, the insolubility of the alcohol ester (S) in the medium shifts the balance and ultimately results in the formation of alcohol ester (S) with a yield clearly greater than 50%.

The crystallized alcohol ester primer (S) has, in practice, been obtained by esterification of the alcohol (S) a-cyano 3-phenoxy-benzyl with D 2-isopropyl 2- acid chloride. para-chlorophenylacetic (see example 3 of the experimental part).

The compounds of general formula (I) which are the subject of the invention have interesting insecticidal properties which make them suitable for use in the fight against insects in the domestic and agricultural fields.

They have a significantly higher insecticidal activity than the corresponding known compounds whose asymmetric carbons have not been split.

They are particularly suitable for application to the fight against insects in the agricultural field. For example, they can effectively fight against aphids, lepidopteran larvae, beetles. They can also be used as insecticides in the domestic field (flies, mosquitoes).

The subject of the invention is also insecticide compositions, characterized in that they contain as active principle at least one of the compounds of general formula (I).

The active ingredient (s) can optionally be added with one or more other pesticidal agents. These compositions can be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible strips, baits or other preparations conventionally used for the use of this kind of compounds.

In addition to the active principle, these compositions generally contain a vehicle and / or a non-ionic surfactant, ensuring, moreover, a uniform dispersion of the constituent substances of the mixture. The vehicle used can be a liquid, such as water,

alcohol, hydrocarbons or other organic solvents, mineral, animal or vegetable oil, powder, such as talc, clays, silicates, kieselguhr or a combustible solid, such as tabu powder (or marc de pyrethrum).

To enhance the insecticidal activity of the compounds of the invention, they can be added to the conventional synergists used in such cases,

such as 1- (2,5,8-trioxadodecyl 2-propyl 4,5-methylenedioxy) -benzene (or piperonyl butoxide), N- (2-ethylheptyl) bicyclo [2,2-1] 5-heptene 2,3-dicarboximide, piperonylbis-2- (2'-n-butoxy-ethoxy) ethylacetal (or tropital).

The insecticidal compositions according to the invention preferably contain between 0.005 and 10% by weight of active material.

A compound similar to those corresponding to the general formula (I) was already known, but in which the two asymmetric carbons were of racemic configuration.

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The present invention now relates to esters in which the asymmetric carbon of the acid part is split (acids called D or L) and in which the asymmetric carbon of the alcohol part is of configuration (R), configuration (S) or configuration (RS).

These compounds have an original character. Obtaining them requires the prior development of the resolution of racemic 2-isopropyl 2-parachlorophenylacetic acid (DL).

The (S) a-cyano 3-phenoxybenzyl esters of general formula (I) had never been obtained before, their preparation necessitating the use of the alcohol (S) a-cyano 3-phenoxybenzyl, a compound which only comes to be described in the patent application filed in France by the holder on January 31, 1978, under the number 78.02621 and entitled "Optically active substituted benzyl alcohol and its preparation process".

The process of obtaining the D 2-isopropyl acid ester

2-parachlorophenylacetic alcohol (S) a-cyano 3-phenoxybenzyl [hereinafter called alcohol ester (S) a-cyano

3-phenoxybenzylic or, more simply, alcohol ester (S)] by the action of a strong base on the alcohol ester (RS), in a solvent capable of insolubilizing the alcohol ester (S ), is itself usable only if one has beforehand primers of ester of alcohol (S) a-cyano 3-phenoxybenzyle. Multiple experiments have shown that, given the physicochemical characteristics of the alcohol ester (S) α-cyano 3-phenoxybenzyl, the action of a base in a solvent, for example ammonia in l isopropanol, on the alcohol ester (RS) a-cyano 3-phenoxybenzyle, in the absence of an alcohol ester primer (S), did not give rise to the insolublization of the ester d alcohol (S) a-cyano 3-phenoxybenzyl. This confirms that it was, to date, impossible to obtain the acid ester D

2-isopropyl 2-parachlorophenylacetic alcohol (S) a-cyano

3-phenoxybenzylic since, to prepare this ester, it is necessary to have crystallized primers of this compound, primers themselves coming from alcohol ester (S) a-cyano 3-phenoxy-benzyl prepared by esterification with using a compound inaccessible to date: alcohol (S) a-cyano 3-phenoxybenzyl (see example 3 of the experimental part).

An example of preparation of the alcohol (S) a-cyano 3-phenoxybenzyl is described later in the experimental part.

The following are new industrial products:

- D 2-isopropyl 2-parachlorophenylacetic acid,

- L 2-isopropyl 2-parachlorophenylacetic acid, and the chlorides of these acids.

The following examples illustrate the invention without, however, limiting it.

Example 1:

Alcohol ester (RS) a-cyano 3-phenoxybenzylic acid L 2-iso-propyl 2-parachlorophenylacetic acid.

Stage A: Salt of (+) a-phenylethylamine of L 2-isopropyl 2-parachlorophenylacetic acid.

In 41 ethanol at 70% water (by volume), 250 g of DL 2-isopropyl 2-parachlorophenylacetic acid are introduced, stirred, added to the solution obtained 140 g of (+) a-phenylethylamine, observe a precipitation, heating the reaction mixture at reflux, add alcohol at 70% water (by volume) until complete dissolution, allow to cool gently, observe a start of crystallization at around 65 ° C., stir at 20 ° C. for 48 h, isolating the precipitate formed by spinning, washing it with ethanol and obtaining 188.9 g of crude salt of (+) a-phenylethylamine of L 2-isopropyl 2-parachlorophenylacetic acid. Md = + 3.5 ° (c = 0.5% methanol).

Purification:

The 188.9 g of crude product are introduced into 41 ethanol at 70% water (by volume), the mixture is heated to reflux, ethanol at 70% water (by volume) is added, to obtain the total dissolution (i.e. 21),

allowed to cool to 20 ° C, stirred for 20 h at 20 ° C, isolated by wringing out the precipitate formed, washed, dried and obtained 147.9 g of (2-) a-phenylethylamine salt of L 2- acid isopropyl 2-parachlorophenylacetic.

Md = + 4.5 ° (c = 0.8% ethanol), F = 210 ° C (with decomposition).

Stage B: L 2-isopropyl 2-parachlorophenylacetic acid.

In 300 cm3 of methylene chloride is introduced 147.5 g of (+) a-phenylethylamine salt of L 2-isopropyl 2-parachlorophenylacetic acid obtained in stage A, added with stirring 300 cm3 of 2N aqueous acid solution hydrochloric acid, agitates for 15 min, obtains two clear phases, separates them by decantation, extracts the aqueous phases with methylene chloride, washing the organic phases with water, extracts the washing waters with methylene chloride, dries the organic phase, filter, dry concentrate and obtain 94 g of L 2-isopropyl 2-parachlorophenylacetic acid. [a] o = -41.5 ° (c = 0.9% ethanol), F = 105 ° C.

Circular dichroism (dioxane)

As = —4 to 218 nm (max), As = +0.029 to 251 nm (max), As = +0.011 to 259 nm (max), Ae = —0.011 to 263 nm (max), Ae = +0.021 to 267 nm (max), As = —0.018 to 271 nm (maximum), As = +0.04 to 275 nm (maximum), As = —0.008 to 278 nm (maximum).

Stage C: L 2-isopropyl 2-parachlorophenylacetic acid chloride

Stirred at reflux for 4 h, a mixture consisting of 10 g of L 2-isopropyl 2-parachlorophenylacetic acid (obtained in stage B), 50 ml of petroleum ether, 20 ml of thionyl chloride, concentrated to dryness by distillation under reduced pressure and obtained 10.8 g of acid chloride which is used in benzene solution in stage D of the present example.

Stage D: Alcohol ester (RS) a-cyano 3-phenoxybenzylic acid L 2-isopropyl 2-parachlorophenylacetic acid.

5.5 g of a-cyano 3-phenoxybenzyl alcohol (RS) and then, in 15 min, at 20 ° C., 25 cm3 of a benzene solution are introduced into a mixture of 10 cm 3 of benzene and 5 cm 3 of pyridine. of L 2-isopropyl 2-parachlorophenylacetic acid chloride, measuring 24 g per 100 cm3 (corresponding to 6 g of acid), stirred at 20 ° C for 15 h, added water, stirred, separated by decantation aqueous phase, benzene extract, wash the organic phase with water, extract the washing water with benzene, dry the benzene solution, filter, concentrate to dryness by distillation under reduced pressure, chromatograph the residue on silica gel, eluting with a mixture of cyclohexane and acetone (95/5) then cyclohexane and ethyl acetate (95/5) and obtains 6.93 g of alcohol ester (RS) a-cyano 3 -phenoxybenzylic acid L 2-isopropyl 2-parachlorophenylacetic acid.

Md = + 6.1 ° (c = 1% ethanol).

Analysis: C25H2203NC1 (419.88)

Calculated: C 71.51 H 5.28 N3.33 Cl 8.44%

Found: C71.6 H 5.3 N3.2 Cl 8.5%

Ultraviolet spectrum (ethanol)

Inflection at 225 nm (E} = 520), maximum at 267 nm (E} = 48), maximum at 271 nm (E} = 50), maximum at 277 nm (E} = 52); inflection at 284 nm (E} = 36); inflection at 305 nm (E} = 1.5).

Circular dichroism (dioxane)

As = + 0.13 at 280 nm (maximum); As = + 0.17 at 274 nm; As = +0.11 at 267 nm (maximum); As = +0.07 at 260 nm (max); As = +6.25 at 227 nm (maximum).

NMR spectrum (deuterochloroform)

Peaks at 0.65-0.76 ppm; 0.67-0.78 ppm; 0.9-1.0 ppm; 1.0-1.12 ppm; characteristic of isopropyl methyls.

Peaks at 2.0-2.67 ppm; characteristic of isopropyl hydrogen located at asymmetric carbon.

Peaks at 3.15-3.32 ppm; characteristic of hydrogen carried by the asymmetric carbon of the acid.

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Peaks at 6.32-6.35 ppm; characteristic of hydrogen carried by the same carbon as the nitrile group.

Peaks at 6.83-7.58 ppm; characteristic of hydrogens in aromatic rings.

Example 2:

Alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid.

Stage A: Recovery of the mixture of D 2-isopropyl 2-parachlorophenylacetic acid and DL 2-isopropyl 2-parachlorophenylacetic acid.

The resolving and purification mother liquors previously obtained in Example 1 are concentrated to dryness, the residue obtained is suspended in 300 cm3 of methylene chloride, a 2N aqueous hydrochloric acid solution is added with stirring to pH = 1 (i.e. approximately 350 cm3 of 2N solution), stirred, separates the organic phase by decantation, extracts the aqueous phase with methylene chloride, combines the organic phases, washing them with water, extracts the washing water with methylene chloride , dries the organic phase, filters, concentrates to dryness by distillation under reduced pressure and obtains 153.5 g of a mixture of D 2-isopropyl 2-parachlorophenylacetic acid and DL 2-isopropyl 2-parachlorophenylacetic acid.

Stage B: Salt of (-) a-phenylethylamine of D 2-isopropyl 2-parachlorophenylacetic acid.

In 41 ethanol at 70% water (by volume), 153 g of mixture of D 2-isopropyl 2-parachlorophenylacetic acid and DL 2-isopropyl 2-parachlorophenylacetic acid are introduced, added to the solution obtained, in 15 min, 86 g of (-) a-phenylethylamine, bring the mixture to reflux with stirring, add ethanol to 70% water (by volume) until complete dissolution (2.251), allow to cool slowly, stirred for 20 h at 20 ° C., isolates and wrung the precipitate formed, washed it with ethanol, dried it and obtained 168.2 g of crude salt of (-) a-phenylethylamine of D 2-isopropyl 2 acid -parachlorophenyl-acetic.

Md = - 5 ° (c = 0.6% methanol)

Purification:

168 g of crude salt of (-) a-phenylethylamine of D 2-isopropyl 2-parachlorophenylacetic acid are introduced into 41 of aqueous ethanol solution at 70% water (by volume), the mixture is brought to reflux, add 70% water ethanol (by volume) until complete dissolution (1.51), allow to cool to 20 ° C, stir at 20 ° C for 48 h, isolate the precipitate formed by wringing , washed with ethanol, dried and obtained 143.1 g of (-) a-phenylethylamine salt of D 2-isopropyl 2-parachlorophenylacetic acid.

Md = —5 ° (c = 0.8% methanol), F = 210 ° C (with decomposition).

Stage C: D 2-isopropyl 2-parachlorophenylacetic acid.

Using a procedure analogous to that of stage B of example 1, starting from 143 g of (-) a-phenylethylamine salt of D 2-isopropyl 2-parachlorophenylacetic acid obtained in stage B of example 2, 91 g of D 2-isopropyl 2-parachlorophenylacetic acid are obtained.

[a] !, 0 = + 42 ° (c = 1% ethanol), F = 105 ° C.

Stage D: D 2-isopropyl 2-parachlorophenylacetic acid chloride.

10 g of D 2-iso-propyl 2-parachlorophenylacetic acid are introduced into a mixture of 50 cm3 of petroleum ether (bp 35-70 ° C) and 20 cm3 of thionyl chloride reflux, maintains it there for 4 h, cools, concentrates to dryness under reduced pressure and obtains 10.8 g of D 2-isopropyl 2-parachlorophenylacetic acid chloride.

Stage E: Alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid.

5.5 g of alcohol (RS) a-cyano 3-phenoxybenzylic alcohol are introduced into a mixture of 10 cm3 of benzene and 5 cm3 of pyridine and then, at 20 ° C., 6 g of D 2 acid chloride -isopropyl 2-parachlorophenylacetic dissolved in 20 cm3 of benzene, stirred at 20 ° C for 15 h, added water, stirred, left to stand, decanted, extracted the aqueous phase with benzene, washed the organic phase with water , extract the washing water with benzene, dry the benzene solution, filter, concentrate to dryness by distillation under reduced pressure, chromatograph the residue on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (95/5 ) and obtains 8.57 g of alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid.

Md = - 5 ° (c = 1.2% ethanol).

Analysis: C25H2203NC1 (419.88)

Calculated: C 71.51 H 5.28 N 3.33 Cl 8.44%

Found: C71.5 H 5.3 N 3.3 Cl 8.6%

Ultraviolet spectrum (ethanol)

Inflection at 225 nm (E} = 534), e = 22400, inflection at 260 nm (E | = 36), inflection at 269 nm (E} = 48), inflection at 272 nm (E} = 50), maximum at 278 nm (E | = 53), 8 = 2200, inflection at 283 nm (E} = 40).

Circular dichroism (dioxane)

As = —0.13 at 282 nm (max); As = - 0.17 at 274 nm (max); As = —0.12 to 267 nm (max); As = —0.08 at 258 nm (max); As = —6.78 at 228 nm (max).

NMR spectrum (deuterochloroform)

Peaks at 0.62-0.73 ppm, 0.63-0.75 ppm, 0.88-0.98 ppm.

Peaks at 0.98-1.05 ppm; characteristic of isopropyle methyls.

Peaks at 1.92-2.66 ppm; characteristic of the isopro-pyle hydrogen located at asymmetric carbon.

Peaks at 3.16-3.33 ppm; characteristic of hydrogen carried by the asymmetric carbon of the acid.

Peaks at 6.32-6.36 ppm; characteristic of hydrogen carried by the same carbon as the nitrile group.

Peaks at 6.83-7.58 ppm; characteristic of hydrogens of aromatic rings.

Example 3:

Ester of alcohol (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid.

In 50 cm3 of benzene, 3 g of (S) a-cyano 3-phenoxybenzyl alcohol, 3.1 g of D 2-isopropyl 2-parachlorophenylacetic acid chloride, introduced as in Stage D of the example, are introduced. 2, cools to + 15 ° C, introduced dropwise a mixture of 4 cm3 of pyridine and 10 cm3 of benzene, stirred for 2 h at 20 ° C, poured onto a 2N aqueous solution of hydrochloric acid, separated by decanting the organic phase, drying, filtering, concentrating to dryness by distillation under reduced pressure, chromatographing the residue on silica gel, eluting with benzene and obtaining 4.4 g of alcohol ester (S) a-cyano 3 -phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic.

Md = + 13.15 ° (c = 2% benzene). This product crystallizes. M = 62 ° C.

Analysis: C25H22C1N03 (419.88)

Calculated: C 71.50 H 5.28 Cl 8.44 N3.34%

Found: C71.4 H 5.3 Cl 9.1 N3.3%

Circular dichroism (dioxane)

As = +0.1 at 253 nm (max); As = +0.23 at 277 nm (max); As = +0.27 at 282 nm (max); As = +0.27 at 286 nm (max).

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NMR spectrum (deuterochloroform)

Peaks at 0.63-0.75 ppm; 0.88-1.0 ppm; characteristic of isopropyl methyl hydrogens.

2.25 ppm peaks; characteristic of the hydrogen of isopropyl carried by carbon has asymmetric carbon.

Peaks at 3.17-3.33 ppm; characteristic of hydrogen carried by the asymmetric carbon of the acid.

Peaks at 6.4 ppm; characteristic of the hydrogen carried by the carbon has a of the nitrile group.

Peaks at 6.91-7.58 ppm; characteristic of hydrogens in aromatic rings.

The alcohol (S) a-cyano 3-phenoxybenzyl can be prepared as follows:

Stage A: Mixture of (IR, 5S) 6,6-dimethyl 4 (R) [(S) -cyano (3'-phenoxyphenyl) methoxy] 3-oxabicyclo [3.1.0] hexan-2-one and of (IR .5S) 6,6-dimethyl 4 (R) [(R) -cyano (3'-phenoxyphenyl) meth-oxy] 3-oxabicyclo [3.1.0] hexan-2-one.

22.5 g of alcohol (RS) a-cyano 3-phenoxybenzylic acid, 9.46 g of lactis of eis 2,2-dimethyl 3 (S) - (dihydroxymethyl) -cyclopropane-1 R-carboxylic acid are mixed 0.150 g of paratoluenesulfonic acid monohydrate, brought to 80 ° C., under a vacuum of 10-2 mm of mercury, maintains the reaction mixture for 2 h under these conditions, the water formed being removed by distillation. Cool to 20C'C and obtain 30.70 g of crude mixture of (IR, 5S) 6,6-dimethyl 4 (R) [(S) -cyano (3'-phenoxyphenyl) methoxy] 3-oxabicyclo [3.1. 0] hexan-2-one and of (IR, 5S) 6,6-dimethyl 4 (R) [(R) -cyano (3'-phen-oxyphenyl) methoxy] 3-oxabicyclo [3.1.0] hexan-2 -one (mainly containing unreacted starting materials as impurities) (mixture A).

Stage B: [1R.5S] 6,6-dimethyl 4 (R) [(S) -cyano (3'-phenoxy-phenyljmethoxy] 3-oxabicyclo [3.1.0] hexan-2-one.

The mixture A obtained in Stage A is chromatographed on silica gel, eluting with a mixture of benzene and ethyl acetate (95/5), to obtain 10.9 g of [IR, 5S] 6,6-dimethyl. 4 (R) [(S) -cyano (3'-phenoxyphenyl) methoxy] 3-oxabicyclo [3.1.0] hexan-2-one.

Mp 126 ° C; [a & ° = -71 ° (c = 1% benzene).

Ultraviolet spectrum (ethanol)

Inflection at 226 nm (E} = 319); inflection at 267 nm (E | = 52); inflection at 271 nm (EJ = 56); maximum at 276 nm (E} = 60); inflection at 280 nm (E} = 46).

Circular dichroism (dioxane)

Ae = —4.2 at 225 nm (max);

Ae = +0.39 at 287 nm (max).

NMR spectrum (deuterochloroform)

Peaks at 1.18-1.23 ppm; characteristic of hydrogens of twin methyls.

Peaks at 1.98-2.08 and 2.15-2.25 ppm; characteristic of isopropyl hydrogens.

Peaks at 5.53-5.54 ppm; characteristic of hydrogen carried by the same carbon as the nitrile group, and of hydrogen in position 4.

Stage C: Alcohol (S) a-cyano 3-phenoxybenzyl.

10 g of (IR, 5S) 6,6-dimethyl 4 (R) [(S) -cyano (3'-phenoxy-phenyl) methoxy are introduced into a mixture of 100 cm 3 of dioxane and 50 cm 3 of water ] 3-oxabicyclo [3.1.0] hexan-2-one, obtained in the preceding stage B, then 1 g of paratoluenesulfonic acid monohydrate,

brings the reaction mixture to reflux, maintains it there for 23 h, concentrates by distillation under reduced pressure, until half the initial volume is obtained, adds ethyl ether, agitates, separates the organic phase by decantation, washing it with water, dry, concentrate to dryness by distillation under reduced pressure, chromatograph the residue (9.5 g) on silica gel, eluting with a mixture of benzene and ethyl acetate (9/1 ) and obtains 6.1 g of alcohol (S) a-cyano 3-phenoxybenzyl.

[a] g> = —16 ° 5 + 1 ° 5 (c = 0.8% benzene).

NMR spectrum (deuterochloroform)

Peaks at 3.25 ppm; characteristic of hydrogen of the alcohol function.

Peaks at 5.41 ppm; characteristic of hydrogen carried by the same carbon as the nitrile group.

Example 4:

Ester of alcohol (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid.

31.5 g of alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid are introduced into a mixture of 60 cm3 of isopropanol and 2 cm3 of triethylamine stirred for 24 h at 20 ° C, for 24 h at 0 ° C, started by adding a small amount of alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic acid (crystallized F = 62 ° C), stirred for 24 h at 0 ° C, then for 48 h at -10 ° C, isolates by spin the precipitate formed, dries it and obtains 6.1 g of first jet, F = 62 ° C.

The mother liquors are concentrated to dryness by distillation under reduced pressure, added to the residue 60 cm3 of petroleum ether (bp = 35-75 ° C) and 10 cm3 of isopropanol, added 2 cm3 of concentrated aqueous ammonia solution at 22 ° C, stirred for 72 h at - 10 ° C,

isolates the precipitate formed by spinning, washing it, drying it and obtaining 13.5 g of second jet (mp = 62 ° C.).

The two jets previously obtained are combined and crystallized from isopropanol. 17.9 g of alcohol ester (S) α-cyano 3-phenoxybenzyl of D 2-isopropyl 2-parachlorophenyl-acetic acid are obtained, mp = 62 ° C.

Example 5:

Insecticide composition:

An insecticidal composition was prepared in the form of an emulsifiable concentrate by homogeneously mixing:

- Alcohol ester (S) a-cyano 3-phenoxybenzylic acid D

2-isopropyl 2-parachlorophenylacetic 0.3 g

- Piperonyl butoxide 0.5 g

- TopanolA 0.1g

- Xylene 99.1 g

Example 6:

Smoke composition:

We homogeneously mix:

- Alcohol ester (S) a-cyano 3-phenoxybenzylic acid D

2-isopropyl 2-parachlorophenylacetic, 1 g

- Tabu powder 25 g

- Cedar leaf powder 39.25 g

- Pine wood powder 33.75 g

- Brilliant green 0.5 g

- p-Nitrophenol 0.5 g

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r

Claims (17)

637,371 2 1. Esters of a-cyano 3-phenoxybenzylic alcohol and 2-isopropyl 2-parachlorophenylacetic acid, of general formula: HjC CH.j cn ci in which the acid residue is in the D or L form and has an asymmetric carbon of determined configuration, and in which the alcoholic residue has an asymmetric carbon of configuration (R), configuration (S) or racemic . 2. As a compound according to claim 1, the alcohol ester (RS) a-cyano 3-phenoxybenzylic acid L 2-isopropyl 2-parachlorophenylacetic acid. 3. As a compound according to claim 1, the alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-para-chlorophenylacetic. 4. As a compound according to claim 1, the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic. 5. As a compound according to claim 1, the alcohol ester (S) a-cyano 3-phenoxybenzylic acid L 2-isopropyl 2-parachlorophenylacetic acid. 6. As a compound according to claim 1, the alcohol ester (RS) a-cyano 3-phenoxybenzylic acid L 2-isopropyl 2-para-chlorophenylacetic acid, determined steric configuration and ao = + 6.1 ° (c = 1% in ethanol). 7. As a compound according to claim 1, the alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-para-chlorophenylacetic acid, determined steric configuration and a ^ = - 5 ° (c = 1.2% in ethanol). 8. As a compound according to claim 1, the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic crystallized. 9. As a compound according to claim 1, the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic, in the pure state, crystallized, of melting point 62 ° C and adj} = + 13.15 ° (c = 2% in benzene). 10. Process for preparing the esters of general formula (I) according to one of claims 1 to 9, characterized in that the DL 2-isopropyl 2-parachlorophenylacetic acid is reacted either with (+) a- phenylethylamine to obtain, after crystallization from a mixture of water and ethanol, the (+) a-phenylethylamine salt of L 2-isopropyl 2-parachlorophenylacetic acid, either with (-) a-phenylethylamine, to obtain, after crystallization from a mixture of water and ethanol, the salt of (-) a-phenylethylamine of D 2-isopropyl 2-parachlorophenylacetic acid, acts on the salt obtained an acid, in the presence of water, to obtain L 2-isopropyl 2-parachlorophenylacetic acid or D 2-isopropyl 2-parachlorophenylacetic acid, and reacts one of these optically active acids, or a functional derivative of this acid with α-cyano 3-phenoxybenzyl alcohol of configuration (R), configuration (S) or configuration (RS), or with a metallic or halogenated derivative of this alcohol. 11. A method of preparation according to claim 10 of the alcohol ester (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic, characterized in that the acid D is reacted 2-isopropyl 2-parachlorophenylacetic with thionyl chloride within benzene, subjects the chloride of D 2-isopropyl 2-parachlorophenylacetic acid resulting from the action of alcohol (RS) a-cyano 3-phenoxybenzyl within benzene, in the presence of pyridine. 12. A method of preparation according to claim 10 of the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic, characterized in that the acid D is reacted 2-isopropyl 2-parachlorophenylacetic with thionyl chloride, within benzene, subjects the chloride of D 2-isopropyl 2-parachlorophenylacetic acid resulting to the action of alcohol (S) a-cyano 3-phenoxybenzyl, within benzene, in the presence of pyridine. 13. A method of preparation according to claim 10 of the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic, characterized in that the ester is subjected alcohol (RS) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic to the action of a basic agent within a solvent or a mixture of solvent in which the ester of alcohol (S) is insoluble. 14. The method of claim 13, wherein the basic agent is ammonia. 15. The method of claim 13, wherein the solvent is isopropanol. 16. Insecticidal compositions, characterized in that they contain, as active principle, at least one of the compounds of general formula (I) according to one of claims 1 to 9. 17. Insecticidal compositions according to claim 16, characterized in that they contain, as active ingredient, the alcohol ester (S) a-cyano 3-phenoxybenzylic acid D 2-isopropyl 2-parachlorophenylacetic.