CH638179A5 - ESTERS OF CARBOXYLIC CYCLOPROPANE ACIDS CARRYING A CHLORINATED OR BROMINATED CHAIN, PREPARATION METHOD AND INSECTICIDE COMPOSITIONS. - Google Patents

Description

The subject of the present invention is a narrow group of new compounds, which differ from those already described in the patent mentioned above by the nature, the degree and the similarity of their pharmacological and biological properties to each other.

The compounds according to the invention are in the form of stereoisomer A, of stereoisomer B or of a mixture of these stereoisomers and they correspond to the formula:

CH.

.COOR

■ CH.

X

In the above formula, R represents a 3,4,5,6-tetra-hydrophthalimidomethyl group and Xj and X2 each represent a bromine atom, the compounds having the configuration (1R, eis) and (IR, trans), or R represents a group (S) a-cyano 3-phenoxybenzyl and Xi and X2 each represent a chlorine atom where Xt represents a bromine atom and X2 a chlorine atom, the compounds having the configuration (1R, eis), or Xj represents a chlorine atom and X2 a bromine atom, the compound having the configuration (IR, trans), or R represents a group (R) a-cyano 3-phenoxybenzyle, X, represents a chlorine atom and X2 an atom bromine, the compound having the configuration (IR, trans).

These compounds are therefore:

- (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromo-ethyl) cyclopropane-l-carboxylate of (S) a-cyano 3-phenoxybenzyl,

- (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dibromo r, 2'-dichloroethyl) -cyclopropane-l-carboxylate of (S) a-cyano 3-phenoxybenzyl,

- 3,4,5,6-tetrahydrophthalimido-methyl (IR, trans) 2,2-dimethyl 3- (r, 2 ') 2', 2'-tetrabromoethyl) -cyclopropane-l-carboxylate,

- 3,4,5,6-tetrahydrophthalimidomethyl (IR, eis) 2,2-dimethyl 3- (r, 2 ', 2', 2'-tetrabromoethyl) cyclo-propane-l-carboxylate,

- (IR, eis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclo-propane-1-carboxylate of (S) a-cyano 3-phenoxybenzyl,

- (R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromo-ethyl) cyclopropane-l-carboxylate from (R) a-cyano 3-phenoxybenzyl.

These compounds are referred to in the following as compounds y.

The (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl 1) -cyclopropane-l-carboxylate of (S) a-cyano 3-phenoxybenzyl has already been described in the patent mentioned. (S, a-cyano 3-phenoxybenzyl) (IR, trans) (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dibromo l', 2'-dichloroethyl) cyclopropane-l-carboxylate ) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1-carboxylate of (S) a-cyano 3-phenoxybenzyl can be prepared by esterification of the corresponding acids, described in patent mentioned, with (S) a-cyano 3-phenoxybenzyl alcohol, according to a process analogous to that described below in Example 3. (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dichloro r, 2'-dibromoethyl) cyclopropane-l-carboxylate of (R) a-cyano 3-phenoxybenzyl can be prepared by esterification of the corresponding acid, described in the mentioned patent, with alcohol (R) a-cyano 3-phenoxybenzyle, according to a process analogous to that described below in Example 6.

The subject of the invention is in particular the compounds y in the form of a mixture of stereoisomers of structure eis and of structure trans in any proportions.

Among these mixtures of compounds, mention will be made more particularly of those which consist of mixtures of stereoisomers of structure eis and of structure trans in the weight proportions 20:80, 50:50 or 80:20.

The subject of the invention is also a process for preparing the compounds y or mixtures of eis and trans isomers according to the above, characterized in that an ester of formula is reacted:

.COOR

C — CH.

in which Xj and R represent the substituents of the compounds of formula I, with an agent capable of fixing Cl2 or Br2 on the double bond of the side chain.

As halogenating agent for esters II, chlorine or bromine is used in particular, and the halogenation for esters II is then carried out in an organic solvent which does not react with chlorine or bromine, such as acid. acetic, carbon tetrachloride, chloroform, methylene chloride.

The subject of the invention is also a process for preparing the compounds y or mixtures defined above, characterized in that an acid of formula:

CH

COOH

C — CH.

in which X1 and R represent the substituents of the compounds of formula I, with an agent capable of fixing Cl2 or Br2 on the double bond of the side chain, then the acid obtained is reacted, of formula:

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CH.

.COOH

• CH.

in which X2 represents the halogen attached to the double bond, or a functional derivative of this acid with an alcohol ROH or one of its functional derivatives, R having the meanings of the corresponding compounds therein.

As an acid halogenating agent III, chlorine or bromine is used in particular, and the halogenation of acids III is then carried out in an organic solvent which does not react with chlorine or bromine, such as acid. acetic, carbon tetrachloride, chloroform, methylene chloride.

The functional derivative of IV acid, used to perform esterification with alcohol ROH or with a functional derivative of this alcohol, is in particular chloride, anhydride, a mixed anhydride, an ester (alkyl lower), a metal salt or an organic base salt of acid III, the functional derivative of the alcohol possibly being a chloride, a bromide or a sulfonate of this alcohol.

The compounds have a high insecticidal activity there which can be demonstrated in particular by tests on flies, on larvae of Spodoptera littoralis, â'Epilachna varivestris, à'Aedes aegypti, Blattella germanica, Dysdercus fasciatus, Sitophilus granarius and Tribolium castaneum.

Endowed with a great photochemical stability, the compounds are suitable there for the application of the fight against insects in the agricultural field. For example, they can effectively fight against aphids, lepidopteran larvae, beetles.

They are then preferably used in doses of between 1 and 100 g of active ingredient per hectare. By their rapidity of action, these compounds can also be used as insecticides in the domestic field.

The subject of the invention is also the insecticidal compositions, characterized in that they contain, as active principle, at least one of the compounds y, or at least one of the mixtures of stereoisomers described above.

In these compositions, 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 type of compound.

In addition to the active principle, these compositions generally contain a vehicle and / or a nonionic surfactant ensuring, in addition, 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, a mineral, animal or vegetable oil, a powder, such as talc, clays, silicates, kieselguhr or a combustible solid, such as tabu powder (or pyrethrum marc).

To enhance the insecticidal activity of the compounds of the invention, conventional synergists used in such cases, such as l- (2,5,8-trioxadodecyl 2-propyl 4,5-methylenedioxy) benzene (or piperonyl butoxide), N- (2-ethylheptyl) bicyclo [2,2, l] -5-heptene-2,3-dicarboximide, lepiperonylbis-2- (2'-n-butoxyethoxy) -ethylacetal (or tropital) .

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

The invention therefore also relates to insecticide compositions as defined above, characterized in that they contain, in addition to the active ingredient (s), a synergizing agent and in particular those containing, as synergizing agent, piperonyl butoxide.

The invention more particularly relates to insecticide compositions as defined above, characterized in that the active principle is (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2 ' -dibromoethyl) cyclopropane-1-carboxylate of (S) a-cyano 3-phenoxybenzyl in the form of isomer A, isomer B or a mixture of these isomers A and B.

The compounds also have an acaricidal activity there which can be demonstrated, in particular, by tests on Tetranychus urticae, as well as a nematicidal activity. A subject of the invention is therefore also acaricide compositions and ne-maticide compositions, characterized in that they contain, as active principle, at least one of the compounds y or at least one of the mixtures of stereoisomers described above.

For acaricide use, wettable powders for foliar spraying containing from I to 80% by weight of active material or liquids for foliar spraying containing from 1 to 500 g / l of active principle are preferably used. It is also possible to use powders for leaf dusting containing from 0.05 to 3% of active material.

For nematicidal use, liquids are preferably used for soil treatment containing 300 to 500 g / 1 of active ingredient.

The acaricide and nematicide compounds according to the invention are preferably used in doses of between 1 and 100 g of active ingredient per hectare.

The anti-mite properties of the compounds according to the invention, as mentioned above, also make it possible to use these products in the form of acaricide compositions for veterinary use, in the fight against parasitic mites of animals and, in particular, in the fight against ixodidae and parasitic sarcoptidae of animals.

The compounds according to the invention can be used in animals to fight in particular against all kinds of scabies, such as sarcoptic scabies, psoroptic scabies and chorioptic scabies.

The compounds according to the invention also make it possible to fight against all kinds of ticks such as, for example, the Boophi-lus species, the Hyalomnia species, the Amblyoma species and the Rhipicephalus species.

The invention therefore also relates to acaricide compositions for veterinary use used in the fight against conditions caused by mites and characterized in that they contain, as active material, at least one of the compounds of formula y or at least one of mixtures of stereoisomers described above.

Said compositions can be used externally, but also parenterally or digestively.

Said compositions can also be advantageously added with a pyrethroid synergizing agent. Such an agent has been defined previously. These compositions are prepared according to the usual methods.

It may be convenient, for veterinary use, to use the compositions according to the invention in admixture with balanced compound feeds.

The following examples illustrate the invention.

Example 1:

(1R, eis) 2,2-Dimethyl 3- (1 ', 2', 2 ', 2'-têtrabromoêthyl) cyclo-

3,4,5,6-tetrahydrophthalimidomethyl propane-1-carboxylate

Stage A: Acid (IR, eis) 2,2-dimethyl3- (1 ', 2', 2 ', 2'-tetrabromo-ethyl) cyclopropane-1-carboxylic:

19.4 g of (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid are added to 150 cm 3 of carbon tetrachloride, 10.4 g of bromine dissolved in 22 cm3 of carbon tetrachloride, stirred for 1 h at 20 ° C, concentrated to dryness by distillation under reduced pressure and obtained 31.4 g of crude product (M = 145 ° C). This crude product is recrystallized from 110 cm3 of carbon tetrachloride and 22.12 g of acid (IR, eis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) are obtained. ) cyclopropane-1-carboxylic (M = 150 ° C).

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This product is a mixture of two isomers A and B which are highlighted by the NMR spectrum. Indeed, the NMR spectrum makes it possible to detect a compound (corresponding approximately to the% of the mixture) having peaks at 1.31-1.43 ppm corresponding to the hydrogens of the twin methyls and peaks from 5.33 to 5.66 ppm corresponding to the hydrogen attached to the asymmetric mono-brominated carbon and another compound (corresponding to approximately 'A of the mixture) having peaks at 1.28-1.48 ppm corresponding to the hydrogens of the twin methyls and peaks of 4, 24 to 5.34 ppm corresponding to the hydrogen fixed on the asymmetric mono-brominated carbon.

In the mixture, moreover, peaks of 1.67 to 2.17 ppm are detected (hydrogens in positions 1 and 3 of cyclopropane) and a peak towards 11.25 ppm (mobile hydrogen of the acid function).

The analysis of the mixture obtained (F = 150 ° C) is as follows:

Analysis for CaH10Br4O2 (PM = 457.804)

Calculated: C 20.99 H 2.20 Br 69.82%

Found: C20.9 H 2.2 Br70.2%

Stabe B: Acid chloride (1R, eis) 2,2-dimethyl 3- (I ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylic:

0.2 cm3 of dimethylformamide, 8.5 cm3 of thionyl chloride are introduced into petroleum ether (bp 35-75 ° C.) in 179 cm 3, the mixture is brought to reflux and 35.76 g of acid are introduced. (IR, eis) 2,2-dimethyl 3- (r, 2 ', 2', 2'-tetrabromoethyl) cyclopropane-l-carboxylic acid in 150 cm3 of methylene chloride, stirred for 2 h at reflux, cooled, concentrated to dry by distillation, add toluene, concentrate again to dryness by distillation under reduced pressure and obtain 38 g of crude acid chloride (Mp = 88 ° C.) used as it is for the following stage.

Stage C: (IR, eis) 2,2-Dimethyl3- (1 ', 2', 2 ', 2'-tetrabromoethyl) -cyclopropane-l-carboxylate of 3,4,5,6-tetrahydrophthalimidomethyl:

7.7 g of acid chloride prepared in the preceding stage are mixed with 2.9 g of neopynaminol in 50 cm 3 of anhydrous benzene, cooled to 0 ° C., introduced with stirring 3 g of pyridine, leaves to return to room temperature while maintaining 1 stir for 18 h, pour the reaction mixture into a dilute hydrochloric acid solution, extract with benzene, wash with an aqueous solution of sodium bicarbonate, rinse with water until neutral, isolate the organic phase, dried over magnesium sulfate, filtered and concentrated under reduced pressure, obtains 10 g of crude product which is purified by chromatography on silica (eluent: benzene / ethyl acetate 95: 5), collects 3.3 g of (IR, eis) 2,2-dimethyl 3- (r, 2 ', 2', 2'-tetrabromo-ethyl) cyclopropane-l-carboxylate of 3,4,5,6-tetrahydrophthalimido-methyl as a mixture of isomers A and B and 0.5 g in the form of isomer B

Characteristics of the product obtained in the form of a mixture of isomers A and B:

[ct] $ = -21.5 ± 1 ° (c = 1%, benzene)

Analysis for CnHigB ^ IW ^ (PM = 620.982)

Calculated: C 32.88 H 3.08 N2.25 Br 51.47%

Found: C33.8 H 3.2 N2, l Br50.2%

UV spectrum (ethanol)

Infi.

= 218 nm

El

= 243

Max.

= 223 nm

Ei

= 275

8 =

17100

Max.

= 229 nm

El

= 269

S =

16700

Infi.

= 238 nm

El

= 170

e =

10500

Infi.

295 nm

El

= 8

NMR spectrum (deuterochloroform)

Peaks at 4.98-5.17 ppm characteristic of hydrogen in position 1 of the ethyl side chain of the B isomer.

Peaks at 1.2-1.45 ppm characteristic of the hydrogens of the twin isomer methyls of the B isomer.

Peaks at 5.17-5.38 ppm characteristic of hydrogen in position 1 'of the ethyl side chain of isomer A.

Peaks at 1.2-1.38 ppm characteristic of the hydrogens of the twin methyls of the A isomer.

Peaks at 1.58-2.08 ppm characteristic of cyclo-propyl hydrogens and cyclohexyl methylenes.

Mass at 2.33 ppm characteristic of the hydrogens of the methylenes of cyclohexyl.

Peaks at 5.33-5.70 ppm characteristic of the hydrogens of the COOCH2N group.

Characteristics of the product obtained in the form of isomer B: [a] 2D ° = +72.5 ± 2.5 ° (c = 0.5%, benzene)

Analysis for C17H19Br4N04 (PM = 620.982)

Calculated: C 32.88 H 3.08 N2.25 Br 51.47%

Found: C 33.5 H 3.3 N2.2 Br50, l%

UV spectrum

Infi. =

218 nm

El

= 248

Max. =

223 nm

El

= 278

Max. =

228-229 nm

El

= 272

Infl. =

238 nm

E1

= 172

Infi.

295 nm

El

= 7

NMR spectrum (deuterochloroform)

Peaks at 4.98-5.16 ppm characteristic of hydrogen in position 1 of the ethyl side chain.

Peaks at 1.21-1.45 ppm characteristic of hydrogens in twin methyls.

Peaks at 1.5-2 ppm characteristic of cyclopropyl hydrogens and methylenes at ß in cyclohexyl.

Mass at 2.38 ppm characteristic of the hydrogens of the methylenes of cyclohexyl.

Peaks at 5.38-5.57 and at 5.57-5.75 ppm characteristic of the hydrogens of the COOCH2N group.

Example 2:

(IR, trans) 2,2-Dimethyl 3- (V, 2 ', 2', 2'-tetrabromoethyl) cyclo-

3,4,5,6-tetrahydrophthalimidomethyl propane-l-carboxylate

Stage A: Acid (IR, trans) 2,2-dimethyl3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylic:

This compound is obtained by bromination of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid, mixture of isomers A and B.

NMR spectrum

Peaks of 1.30 to 1.40 ppm (hydrogen halides of 2-cyclopropane).

Peaks at 1.65-1.74 and 1.97-2.37 ppm (hydrogens in 1 and 3 of cyclopropane).

Peaks at 4.30-4.47 and 4.47-4.65 ppm (hydrogen to ethyl).

Peak at 9.63 ppm (hydrogen from the carboxyl).

Stage B: Acid chloride (IR, trans) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylic:

By the action of thionyl chloride on the acid (IR, trans) 2,2-dimethyl 3- (r, 2 ', 2', 2'-tetrabromoethyl) cyclopropane-1-carboxylic obtained in stage A, the chloride is obtained of acid used as in the next stage.

IR spectrum (chloroform)

Absorption at 1778 cm-1.

Stage C: (IR, trans) 2,2-Dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-l-carboxylate of 3,4,5,6-tetrahydrophthalimidomethyl:

7.7 g of acid chloride prepared in the preceding stage are treated according to a procedure identical to that used in stage C of

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Example 1. 9.2 g of crude product are obtained, which product is purified by chromatography on silica (eluent: benzene / ethyl acetate 9: 1). After crystallization, the product is taken up in petroleum ether (40-70 ° C), drained, dried and recovered 5.4 g of (IR, trans) 2,2-dimethyl 3- (1 ', 2 ', 2', 2'-tetrabromoethyl) cyclopropane-1-3,4,5,6-tetrahydrophthalimidomethylcarboxylate. Mixture of isomers A and B (F = 124 ° C).

Mîî = - 1 ° (c = 1%, benzene)

Analysis for C17Hi9Br4N04 (PM = 620.982)

Calculated: C 32.88 H 3.08 Br 51.47 N2.25%

Found: C33, l H 3.2 Br51, l N2, l%

UV spectrum (ethanol)

Max. = 224 nm E [= 274 s = 17000

Max. = 228 nm E} = 269 8 = 16700

Infi. = 235 nm E {= 167 8 = 10400

Infi. - 280 nm E {= 9

NMR spectrum (deuterochloroform)

Peaks at 1.25-1.30-1.31 ppm characteristic of hydrogens in twin methyls.

Peaks of 1.58 to 2.16 ppm characteristic of the hydrogens of cyclo-propyl and of the methyls in ß in cyclohexyl.

Peaks of 2.16 to 2.5 ppm characteristic of the hydrogens of the methylenes in α in cyclohexyl.

Peaks at 4.24-4.41 and 4.43-4.61 ppm characteristic of hydrogen in position 1 of the ethyl side chain.

Peaks at 5.51 and 5.55 ppm characteristic of the COOCH2N group.

Example 3:

(IR, trans) 2,2-Dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) -cyclopropane-l-carboxylate de (S) a-cyano 3-phenoxybenzyle

Stage A: Acid (IR, trans) 2,2-dimethyl3- (2 ', 2'-dichloro l', 2'-dibromoethyl) cyclopropane-1-carboxylic:

By the action of bromine on (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylic acid, the (1R, trans) 2,2-dimethyl acid is obtained 3- (2 ', 2'-dichloro r, 2'-dibromoethyl) cyclo-propane-1-carboxylic, mixture of isomers A and B.

NMR spectrum

Peaks at 1.17-1.37 ppm (hydrogen halides of 2-cyclopropane).

Peaks of 1.65-1.73 to 1.93-2.03 ppm (hydrogen in 1 of cyclopropane).

Peaks at 4.23-4.45 and 4.45-4.62 ppm (hydrogen in the ethyl of 3 in cyclopropane).

Stage B: Acid chloride (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic:

By the action of thionyl chloride on the acid prepared in step A above, the acid chloride (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-) is obtained. dibromoethyl) cyclopropane-1-carboxylic.

IR spectrum (chloroform)

Absorption at 1177 cm "1.

Stage C: (IR, trans) 2,2-Dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromoethyl) cyclopropane-l-carboxylate of (S) a-cyano 3-phenoxy-benzyl:

4.45 g of the acid chloride prepared in the preceding stage are mixed with 2.6 g of (S) a-cyano 3-phenoxybenzyl alcohol in 100 cm 3 of anhydrous benzene. Cool to 15 ° C, add a solution of 5 cm3 of pyridine in 20 cm3 of anhydrous benzene. Stirring is continued for 3 h at room temperature and the reaction medium is poured onto 100 cm3 of 2N hydrochloric acid, the organic phase is isolated, washed with water and concentrated to dryness under reduced pressure. After

Chromatography on silica (eluent: benzene), 4.9 g of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromoethyl) cyclo-propane-1 are obtained (S) a-cyano 3-phenoxybenzyl carboxylate as a mixture of A and B isomers

[a] = 0 ° (benzene)

Analysis for C22H1!) C1203N (PM = 576.12)

Calculated: C 45.86 H 3.32 Br 27.74 Cl 12.31 N2.43% Found: C46.0 H 3.4 Br27.5 Cl 12.2 N2.2% Circular dichroism

Max. at 287 nm Ae = +0.12 Max. at 282nm As = +0.11 Max. at 265 nm Ae = +0.042

NMR spectrum

Peaks at 1.20-1.26-1.31 ppm characteristic of hydrogens in twin methyls.

Peaks at 4.20-4.35 and at 4.36-4.52 ppm characteristic of hydrogen in position 1 of the ethyl chain.

Peaks of 1.68 to 1.78, 1.97 to 2.07 and 1.97 to 2.42 ppm characteristic of cyclopropyl hydrogens.

Peak at 6.42 ppm characteristic of hydrogen from the COOCHCN group.

Peaks from 6.92 to 7.58 ppm characteristic of hydrogens in aromatic rings.

Stage D: Separation of the A and B isomers of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylate from (S) a-cyano 3-phenoxybenzyl:

Chromatography on silica 4.69 g of the mixture of isomers A and B of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro r, 2'-dibromoethyl) -cyclopropane-1-carboxylate of (S) a-cyano 3-phenoxybenzyl obtained in stage C, eluting with a hexane / pentane / ether / acetonitrile / isopropanol mixture (30: 12: 0.4: 1.2: 0.03) and obtains:

- 1.385 g of isomer A [a] | 5 = + 35.5 ± 2.5 ° (c = 0.5%,

benzene), and

- 0.980 g of isomer B [a] | J = —17.5 + 2 ° (c = 0.8%, benzene). The alcohol (S) a-cyano 3-phenoxybenzyl used in stage C of Example 3 is described in the patent application filed by the licensee on January 31, 1978 under No. 78.02621 and entitled "Optically substituted benzyl alcohol active ingredient and its preparation process ”. An example of the preparation of this alcohol is given below:

Stage A: Mixture of (IR, 5S) 6,6-dimethyl4 (R) [(S) -cyano (3'-phenoxyphenyl) methoxy] 3-oxabicyclo (3-1-0) hexan-2-one and of ( 1R, 5S) 6,6-dimethyl 4 (R) [(R) -cyano (3'-phenenphenphenyl) -methoxy] 3-oxabicyclo (3-1-0) hexan-2-one:

22.5 g of alcohol (R, S) a-cyano 3-phenoxybenzylic acid, 9.46 g of lactone of acid (1R, 3S) -cis 2,2-dimethyl 3- (dihydroxy-methyl) are mixed cyclopropane-1-carboxylic acid, 0.150 g of paratoluene sulfonic 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 eliminated by distillation. Cool to 20 ° C and obtain 30.7 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'-phenoxy-phenyl) methoxy] 3-oxabicyclo (3-1-0 ) hexan-2-one (containing, as impurities, mainly unreacted starting materials) (mixture A).

Stage B: (1R, 5S) 6,6-Dimethyl4 (R) [(S) -cyano (3'-phenoxy-phenyl) methoxy] 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-dimethyl4 ( R) [(S) -cyano (3'-phenoxyphenyl) methoxy] 3-oxabicyclo (3-1-0) hexan-2-one (M = 126 ° C).

Md - —71 ° C (c = 1%, benzene)

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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 stage B above, then 1 g of paratoluene sulfonic acid monohydrate, brings the reaction mixture to reflux, maintains it there for 23 h, concentrated by distillation under reduced pressure until half of the initial volume is added, ethyl ether is added, stirred, the organic phase is separated by decantation, washed with water, dried, concentrated to dryness by distillation under pressure reduced, chromatograph the residue (9.5 g) on silica gel, eluting with a mixture of benzene and ethyl acetate (9: 1), to obtain 6.1 g of alcohol (S) a-cyano 3 -phenoxybenzyl.

[a] = —16.5 ± 1.5 ° (c = 0.8%, benzene)

NMR spectrum (deuterochloroform)

Peak at 2.35 ppm characteristic of hydrogen in the alcohol function.

Peak at 5.42 ppm characteristic of hydrogen carried by the same carbon as the nitrile group.

Example 4:

(IR, eis) 2,2-Dimethyl3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-l-carboxylate de (S) a-cyano 3-phenoxybenzyle

Stage A: Acid (IR, eis) 2,2-dimethyl3- (2 ', 2'-dibromo l', 2'-dichloroethyl) cyclopropane-1-carboxylic:

In 30 cm3 of carbon tetrachloride, 11.8 g of chlorine are introduced by bar-botage at -15 ° C., then 24 g of an acid solution (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dibromo-vinyl) cyclopropane-1-carboxylic acid in 37 cm3 of methylene chloride, stirred for 1 h and 30 min at 0 ° C and for 2 h at 25 ° C, concentrated under reduced pressure, purified by crystallization from carbon tetrachloride and obtained 7.4 g of acid (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dibromo l', 2 ' -dichloroethyl) cyclopropane-1-carboxylic (M = 134 ° C) (mixture of isomers A and B).

NMR spectrum

Peaks at 1.32-1.44 and 1.28-1.46 ppm (hydrogen halides of 2-cyclopropane).

Peaks at 5.08-5.45 and 4.67-5.0 ppm (hydrogen at the end of the ethyl chain in position 3 of the cyclopropane).

Peak at 10.1 ppm (hydrogen from the carboxyl).

Stage B: Acid chloride (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic:

By the action of thionyl chloride in the presence of pyridine on the acid obtained in the preceding stage A, the acid chloride (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dibromo l') is obtained. , 2'-dichloroethyl) cyclo-propane-1-carboxylic acid used as it is for the following stage.

Stage C: (IR, eis) 2,2-Dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylate of (S) a-cyano 3-phenoxybenzyl:

3.8 g of the acid chloride prepared in the preceding stage are mixed with 2.5 g of (S) a-cyano 3-phenoxybenzyl alcohol in 100 cm 3 of anhydrous benzene. Cool to + 15 ° C and add a solution of 4 cm3 of pyridine in 20 cm3 of anhydrous benzene. Stirring is continued for 4 h at room temperature and the reaction medium is poured onto 100 cm3 of 2N hydrochloric acid. The organic phase is isolated, washed with water, dried and concentrated to dryness under reduced pressure.

After chromatography on silica [eluent: petroleum ether (40-70 ° C) / isopropyl ether (100:20)], the (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dibromo) is obtained r, 2'-dichloroethyl) cyclopropane-1-carboxylate of (S) a-cyano 3-phenoxybenzyl, in the form of 1.8 g of isomer A (rf = 0.30) and 1.4 g of isomer B (rf = 0.25).

Physical controls of the A isomer:

Mid? = —21 ± l ° (c = 1%, benzene)

Circular dichroism

Max. at 300 nm

Ae =

-0.003

Max. at 288 nm

Ae =

+0.29

Max. at 264 nm

Ae =

+0.11

Max. at 232 nm

Ae =

-1.8

NMR spectrum (deuterochloroform)

Peaks at 1.28-1.37 ppm characteristic of hydrogens in twin methyls.

Peaks at 5.05-5.10 and 5.18-5.23 ppm characteristic of hydrogen in position 1 of the ethyl side chain.

Peaks at 1.83-2.10 ppm characteristic of cyclo-propyl hydrogens.

Peaks at 6.38 ppm characteristic of hydrogen from the COOCHCN group.

Peaks from 6.92 to 7.55 ppm characteristic of hydrogens in aromatic rings.

Physical controls of the B isomer:

[a] '{5 = + 80 + 2.5 ° (c = 1%, benzene)

Circular dichroism:

Max. at 288 nm Ae = +0.22 Inf. at 263nm Ae = +0.62 Max. at 220 nm Ae = +3.7 NMR spectrum (deuterochloroform)

Peaks at 1.23-1.38 ppm characteristic of hydrogens in twin methyls.

Peaks of 4.6 to 4.95 ppm characteristic of hydrogen in position V of the ethyl side chain.

Peaks of 1.75 to 2.16 ppm characteristic of cyclo-propyl hydrogens.

Peak at 6.38 ppm characteristic of hydrogen from the COOCHCN group.

Peaks of 6.88 to 7.57 ppm characteristic of hydrogens in aromatic rings.

Example 5:

(IR, eis) 2,2-Dimethyl3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-l-carboxylate of (S) a-cyano 3-phenoxybenzyl Stage A: Acid (IR, eis) 2,2-dimethyl3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1 -carboxylic:

In 30 cm3 of carbon tetrachloride, the chlorine is bubbled until saturation (11.8 g of chlorine is dissolved), a solution of 16.7 g of acid is introduced in approximately 30 min (IR, eis) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylic acid in 40 cm3 of methylene chloride at a temperature below 0 ° C, stirred for 24 h at 0 ° C, brings the temperature of the reaction mixture at + 25 ° C, stirred for 3 h at this temperature, removes excess chlorine by bubbling nitrogen through, concentrated to dryness by distillation under reduced pressure, purifies the residue by chromatography on silica gel, eluting with a mixture eyelohexane and ethyl acetate (8: 2), crystallized from petroleum ether (bp 35-75 ° C) and obtained 3.14 g of acid (IR, eis) 2,2-dimethyl 3- (l ', 2', 2 ', 2'-tetrachloroethyl) -cyclopropane-1-carboxylic (M = 144 ° C).

Analysis for * C3Hl0GÏAO2 (279.98)

Calculated: C34.3 H 3.6 Cl 50.6%

Found: C34.4 H 3.7 Cl 50.3%

NMR spectrum (deuterochloroform)

Peaks at 1.26-1.42 and 1.30-1.42 ppm characteristic of hydrogens in twin methyls.

Peaks of 4.67-5.17 and 5.08 to 5.43 ppm characteristic of hydrogen in the ′ position of the substituted ethyl side chain.

Peaks of 1.67 to 2.0 ppm characteristic of cyclo-propyl hydrogens.

Peaks at 10.2 ppm characteristic of carboxyl hydroxide.

s

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8

Stage B: Chloride of the acid (1R, eis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tëtrachloroethyl) cyclopropane-1-carboxylic:

6.75 g of (1R, eis) 2,2-dimethyl acid are introduced into a mixture of 60 cm3 of petroleum ether (bp 35-70 ° C) and 8.7 cm3 of thionyl chloride 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1 -carboxylic, brings the reaction mixture to reflux, keeps it there for 4 h and 30 min, concentrated to dryness by distillation under reduced pressure, add benzene, concentrate to dryness and obtain the acid chloride (IR, eis) 2,2-dimethyl 3- (r, 2 ', 2', 2'-tetrachloroethyl) cyclo-propane-1-carboxylic used as is for the next stage.

Stage C: (IR, eis) 2,2-Dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) -cyclopropane-I-carboxylate of (S) a-cyano 3-phenoxybenzyl:

3.19 g of the acid chloride prepared in the preceding stage are mixed with 2.6 g of (S) a-cyano 3-phenoxybenzyl alcohol in 30 cm 3 of anhydrous benzene. Cooled in an ice bath and slowly add 3 cm3 of pyridine. The mixture is stirred for 24 h at room temperature, then the reaction medium is poured over dilute and cold hydrochloric acid. It is extracted with benzene, the organic phases are isolated, washed with a sodium bicarbonate solution, rinsed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification is carried out by chromatography on silica (eluent: benzene / cyclp-hexane 7: 3) and the (IR, eis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane- is obtained. (S) a-cyano 3-phenoxybenzyl l-carboxylate in the form of 2.258 g of the isomer A and 1.48 g of the mixture of isomers A and B.

Physical analysis of the A isomer:

[a] $ = +35.5 ± 2 ° (c = 0.6%, benzene)

Analysis for C22H19Cl4.N03 (487,213)

Calculated: C 54.23 H 3.93 N2.87 Cl 29.1%

Found: C54.4 H 3.8 N2.8 Cl 28.5%

NMR spectrum (deuterochloroform)

Peaks at 1.28-1.37 ppm characteristic of hydrogens in twin methyls.

Peaks of 1.75 to 2.08 ppm characteristic of the cyclo-propyl hydrogens.

Peaks of 5.07 to 5.25 ppm characteristic of hydrogen in position 1 of the ethyl side chain.

Peak at 6.35 ppm characteristic of the hydrogens of the COOCHCN group.

Peaks of 6.92 to 7.58 ppm characteristic of hydrogens in aromatic rings.

Physical analysis of the mixture of A and B isomers: Mi> = —33.5 + 2.5 ° (c = 0.4%, benzene)

Analysis for C22Hi9C14N03 (487,213)

Calculated: C 54.23 H 3.93 N2.87 Cl 29.1%

Found: C 54.5 H 3.9 N2.8 Cl 28.8%

NMR spectrum (deuterochloroform)

Peaks at 1.2-1.35 ppm characteristic of the hydrogens of the R-isomer twin methyl

Peaks at 1.27-1.35 ppm characteristic of the hydrogens of the twin methyls of the isomer S.

Peaks at 1.75-2.08 ppm characteristic of cyclo-propyl hydrogens.

Peaks of 4.77 to 4.94 ppm characteristic of hydrogen in position 1 of the ethyl side chain.

Peaks of 5.08 to 5.26 ppm characteristic of hydrogen in position 1 of the ethyl side chain.

Peaks at 6.35 and 6.37 ppm characteristic of hydrogen from the COOCHCN group.

Peaks of 7.93 to 7.58 ppm characteristic of hydrogens in aromatic rings.

Example 6:

(IR, trans) 2,2-Dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) -cyclopropane-l-carboxylate from (R) a-cyano 3-phenoxybenzyl

By operating as in stage C of Example 3, starting with 2 g of acid chloride (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2 'dibromoethyl) cyclopropane-1-carboxylic, obtained in stage B of Example 3, and 1.1 g of alcohol (R) a-cyano 3-phenoxybenzyl, 1.4 g of (IR, trans) 2.2 are obtained -dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromoethyl) cyclopropane-1-carboxylate of (R) a-cyano 3-phenoxybenzyl, in the form of a mixture of isomers A and B. Mid? = —28 ± 2 ° (c = 0.7%, benzene)

Analysis for C22H19Br2Cl2N03 (PM = 576,122)

Calculated: C 45.87 H 3.32 N2.43 Cl 12.31 Br 27.74% Found: C46.3 H 3.3 N2.4 Cl 12.4 Br27.4% NMR spectrum (deuterochloroform)

Peaks at 1.31-1.35 ppm characteristic of hydrogens in twin methyls.

Peaks of 1.66 to 2.42 ppm characteristic of cyclo-propyl hydrogens.

Peaks at 4.23-4.42 ppm 1 characteristic of hydrogen in posi-

and at 4.42-4.58 ppm J tioij the ethyl side chain. Peak at 6.47 ppm characteristic of hydrogen from the COOCHCN group.

Peaks of 6.92 to 7.58 ppm characteristic of hydrogens in aromatic rings.

Circular dichroism (dioxane):

Max. at 219 nm e = —5.4 Max. at 280 nm 8 = —0.28 Infi. at 285nm s = —0.27

The mixture of isomers A and B prepared above is chromatographed on silica eluting with a hexane / pentane / ether mixture (7: 2, 8: 0.17) and the A and B isomers are obtained separately.

Isomer A

NMR spectrum (deuterochloroform)

Peaks at 1.32-1.37 ppm characteristic of hydrogens in twin methyls.

Peaks at 1.66-1.76 ppm,

at 2 08 2 17 ppm characteristic of hydrogenated from and at 26-2 ', 35 ppm cyclopropane.

Peaks at 4.2-4.37 ppm characteristic of hydrogen in position 1 '

of the ethyl side chain.

Peak at 6.42 ppm characteristic of the hydrogen in the group

COOCHCN.

Peaks of 6.92 to 7.58 ppm characteristic of hydrogens in aromatic rings.

Isomer B

NMR spectrum (deuterochloroform)

Peaks at 4.37-4.53 ppm characteristic of hydrogen in position 1 of the ethyl side chain.

The alcohol (R) a-cyano 3-phenoxybenzyl, used starting from Example 6, was prepared as follows:

Stage A: (1R.5S) 6,6-Dimethyl4 (R) [(R) -cyano (3'-phenoxy-phenyl) methoxy] 3-oxabicyclo (3-1-0) hexan-2-one:

The chromatography started in Stage B of the preparation described in Example 3 is continued and 7.32 g of expected product is obtained. Md = -120 ± 2.5 ° (c = 0.9%, benzene)

Stage B: Alcohol (R) a-cyano 3-phenoxybenzyl:

The procedure is analogous to that described in stage C of the preparation described in example 3, starting from 12.8 g of product described in the preceding stage and obtaining, after the same purification by chromatography, 5 g of the expected product .

MiS = +11 ± 2 ° (c = 0.5%, benzene)

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638,179

Study of the insecticidal activity of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-l-carboxylate of (S) a-cyano 3-phenoxybenzyl (compound A), of the A isomer of f 1R, eis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylate of (S) a- cyano 3-phenoxybenzyl (compound B) and the isomer B of the same compound (compound C).

1) Study of the lethal activity of compounds A, BetC on houseflies

The test insects are female house flies aged 4 d. One operates by topical application of 1 n of acetoni-only solution on the dorsal thorax of the insects using the micromanipulator of Arnold. 50 individuals are used per treatment. The mortality check is carried out 24 hours after treatment.

The tests are carried out without a synergist or with the addition of piperonyl butoxide (10 parts of synergist for 1 part of compound to be tested).

The experimental results, summarized in the following table, are expressed in LD 50 or dose (in nanograms) necessary to kill 50% of the insects:

LD 50 (ng / insect)

Compound A not synergized

5.75

Compound A synergized

0.91

Compound B not synergized

/

1.67

Compound B synergized

0.88

Compound C not synergized

2.95

Compound C synergized

0.82

Conclusion: Compounds A, B and C are endowed with a strong insecticidal activity against house flies.

2) Study of the knock-down activity of compounds A, B and C on houseflies

The test insects are female house flies aged 4 d. The operation is carried out by direct spraying in a Kearns and March chamber using, as solvent, a mixture in equal volumes of acetone and kerosene (quantity of solution used 2 × 0.2 cm 3). About 50 insects are used per treatment. The controls are carried out every minute until 10 min, then at 15 min, and the KT50 is determined by the usual methods.

The experimental results obtained are summarized in the following table:

KTJ0 (min)

Compound A

6.00

Compound B

6.12

Compound C

6.02

Conclusion: Compounds A, B and C have an interesting know-down power with regard to house flies.

3) Study of the insecticidal activity on house flies of compound A used in the form of a smoke coil

Neutral supports of smoke coils are impregnated with active material in solution in acetone. One releases, in a closed glass cylinder of 13.50 dm3.20 female house flies aged 4 to 5 d and introduced, for 2 min, a smoke smoke coil consuming at one end. The knock-down control is carried out every minute and the test is stopped 5 min after all the insects have been killed. Three series of tests are performed for each dose.

Doses by weight of active ingredient for coil weight kt50

kt50

kts0

kt50

(average)

Compound A

0.4%

7.5

8.8

6.6

7.75

0.2%

11.8

10.2

9.2

10.22

Conclusion: Useful in fumigant composition, compound A shows good insecticidal activity.

4) Study of the insecticidal activity of compounds A, B and C on caterpillars of Spodoptera littoralis

The tests are carried out by topical application. One dj.1 of an acetone solution of the product to be tested is deposited on the dorsal thorax of each individual. 15 caterpillars of Spodoptera littoralis in the 4th larval stage are used for each dose used. After treatment, the individuals are placed on an artificial nutritive medium (Poitoit medium). The effectiveness control is carried out (percentage of mortality taking into account an untreated control) 24 h, then 48 h after treatment, and the lethal dose 50 (LD50) in nanograms per caterpillar is determined.

The experimental results are summarized in the following table:

DLjo (ng / caterpillar)

Compound A

0.22

Compound B

0.57

Compound C

0.65

Conclusion: Compounds A, B and C have a strong insecticidal power against the caterpillars of Spodoptera littoralis.

5) Study of the insecticidal activity on rf'Epilachna varivestris larvae

The tests are carried out by topical application in a manner analogous to that used for the larvae of Spodoptera. Larvae of the penultimate larval stage are used and, after treatment, the larvae are fed by bean plants. The mortality control is carried out 72 hours after treatment.

The experimental results are summarized in the following table:

DLS0 (ng / individual)

Compound A

0.18

Compound B

4.26

Compound C

6.95

Conclusion: Compounds A, B and C are endowed with a strong insecticidal activity on the larvae with Epilachna varivestris. Compound A, in this area, has a particularly marked activity.

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6) Study of the insecticidal activity of compound A on Aedes aegypti larvae

370 ml jars are used into which 200 ml of water are introduced. The water in each jar is treated with 1 ml of acetone solution containing the product to be tested. Each jar is infested with 10 Aedes aegypti larvae (at the last larval stage). The larvae are brought from the roost in 49 ml of water. The effectiveness checks are carried out 24 to 48 hours after the infestation. For the duration of the test, the jars are stored in an oven at 25 ° C.

The results obtained are summarized in the following table:

CLS0 (ppm)

Compound A

3.24 x 10.5 "

Conclusion: Compound A has a strong insecticidal activity on the larvae of Aedes aegypti.

7) Study of the insecticidal activity of compound A on Blattella germanica

This test is performed by topical application. Male adults of Blattella germanica, chosen according to the length criterion, receive 2 µl of acetone solution of the product to be tested between the second and third pair of legs. After treatment, the test insects are stored in the dark at 20 ° C and are fed. Doses of 10-7.5-5-3.75-2.5 ng / insect are used. The controls are carried out 24 h, 48 h and 6 d after treatment.

The experimental results, expressed in LD50 in nanograms per insect, are summarized in the following table:

DLS0 (ng / insect)

Compound A

1.06

Conclusion: Compound A has a strong insecticidal activity against Blattella germanica.

8) Study of the insecticidal activity of compound A with respect to Dysdercus fasciatus

1 (of acetone solution of product to be tested is deposited on the ventral thorax of each individual. Doses of 3.75-2.5-1.25-1-0.625 ng / insect are used. The efficacy controls are performed 24 h, 48 h and 5 d after treatment.

The results obtained are mentioned in the following table:

DLso (ng / insect)

Compound A

1.06

Conclusion: Compound A has a strong insecticidal activity against Dysdercus fasciatus.

9) Study of the insecticidal activity of compound A on Sitophilus granarius and Tribolium castaneum

The test is carried out by direct spraying on infested wheat. 5 ml of acetone solution of product to be tested and 0.1 cm3 of water are sprayed on 100 g of wheat contained in a flask of 11 of a rotary evaporator (in movement). An artificial infestation is carried out with 50 individuals (Sitophilus or Tribolium). For each dose, the percentage of mortality is determined after 7 d by taking an untreated control into account and by averaging over 100 individuals and the lethal concentrations are determined in parts per million.

Doses (ppm)

Sitophilus granarius

Tribolium castaneum

Mortality (%)

cl50

(ppm)

Mortality (%)

CLso (ppm)

1.5

90.0

100

1.0

66.70

96.9

0.75

35.3

0.80

89.5

0.19

0.5

18.2

85.3

0.25

2.0

62.0

Conclusion: Compound A has good insecticidal activity against Sitophilus granarius and Tribolium castaneum.

Study of the acaricidal activity of compound A on Tetranychus urticae

Bean leaves infested with 10 females of Tetranychus urticae are used per leaf and coated with glue at their periphery; the females are left powdered for 24 h, withdraws them and divides the leaves thus infested with eggs in two groups.

a) A first group is treated with the test compound; the operation is carried out by spraying 0.5 cm3 of aqueous solution onto each sheet using concentrations of 50 and 25 g of test compound per hectare.

b) A second group of leaves is not treated and serves as a control group.

The count of live adults, live eggs and live larvae takes place 9 after the start of treatment.

The results, expressed as a percentage of mortality of adults, eggs and larvae, are summarized in the following table (taking into account the untreated control):

Adult mortality (%)

Unhatched eggs (%)

Larval mortality (%)

Compound A

52.3

54.3

47.6

Conclusion: Compound A is endowed with an interesting acaricidal power with regard to Tetranychus urticae.

Example 7;

Insecticide composition

An emulsifiable concentrate was prepared by thoroughly mixing:

- (IR, trans) 2,2-Dimethyl 3 - (', 2'-dichloro l', 2'-dibromo-ethyl) cyclopropane-l-carboxylate de (S) a-cyano 3-

phenoxybenzyl 0.015 g

- Piperonyl butoxide 0.5 g

- TopanolA 0.1g

- Xylene 99.385 g

Example 8:

Insecticide composition

An emulsifiable concentrate was prepared as follows: A homogeneous mixture of:

- (IR, trans) 2,2-Dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromoethyl) cyclopropane-l-carboxylate from (S) a-

cyano 3-phenoxybenzyl 1.5 g

- Tween 80 20 g

- Topanol A 0.1 g

- Xylene 78.4 g

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Example 9:

Miticide composition

An emulsifiable concentrate was prepared containing, by weight, 20% of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromo-ethyl) cyclopropane-1-carboxylate (S) a-cyano 3-phenoxybenzyl, 6.5% by weight of Atlox 4851 (oxyethylenated triglyceride combined with a sulfonate, acid number: 1.5), 3.3% of Atlox 4855 (combined oxyethylenated triglyceride with a sulfonate, acid number: 3) and 70.2% xylene.

Example 10:

Nematicidal composition

An emulsifiable concentrate for soil treatment was prepared containing, by weight, 45% of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromoethyl) cyclopropane-l- (S) a-cyano 3-phenoxybenzyl carboxylate, 6.4% Atlex 4851 (oxyethylenated triglyceride combined with a sulfonate, acid number: 1.5), 3.2% Atlox 4855 and 45.4 % of xylene.

Example 11:

Ixodicide composition

A solution was prepared, the composition of which is as follows:

- (IR, trans) 2,2-Dimethyl 3- (2 ', 2'-dichloro l', 2'-dibro-moethyl) cyclopropane-l-carboxylate de (S) a-cyano 3-

phenoxybenzyl 0.5 g

- Polysorbate 80 10 g

- Triton X 100 25 g

- A-tocopherol acetate 1 g

- Ethanol q.s.p 100 ml30

This solution is used for external use after dilution in 50 times its volume of water.

Example 12:

Ixodicide composition

An injectable solution containing:

- (IR, trans) 2,2-Dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromoethyl) cyclopropane-l-carboxylate from (S) a-

cyano 3-phenoxybenzyl 2 g

- Piperonyl butoxide 6.65 g

- A-tocopherol acetate 0.33 g

- Oily excipient * q.s.p 100 cm3

* This oily excipient is made up of 29 g of benzyl benzoate and peanut oil in sufficient quantity to obtain a total volume of 100 cm3.

Example 13:

Compound feed

As a basic balanced food, a food comprising corn, dehydrated alfalfa, wheat straw, molasses palm kernel meal, urea, a vitamin-mineral mineral condiment is used.

This food contains, at least, 11% of crude protein matter (including 2.8% provided by urea), 2.5% fat and, at most, 15% cellulosic matter, 6% mineral matter and 13% humidity.

The feed used corresponds to 82 fodder units per 100 kg, 910,000 IU of vitamin A, 91,000 IU of vitamin D 3.156 mg of vitamin E and 150 mg of vitamin C.

0.04 kg of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromoethyl) cyclopropane-l-carboxylate from (S) a-cyano is incorporated into this food 3-phenoxybenzyl.

R

Claims (14)

638,179 2 CLAIMS 1. Compounds of formula: CH .COOR ■ CH. X in the form of stereo-isomer A, of stereo-isomer B or of a mixture of these stereoisomers, formula in which R represents a group 3,4,5,6-tetrahydrophthalimidomethyl and X, and X2 each represent a bromine atom, the compounds having the configuration (1R, eis) and (IR, trans), where R represents a group (S) a-cyano 3-phenoxybenzyl and Xj and X2 each represent a bromine atom and X2 a chlorine atom, the compounds having the configuration (1R, eis), where Xj represents a chlorine atom and X2 a bromine atom, the compound having the configuration (IR, trans), where R represents a group (R) a-cyano 3-phenoxybenzyle, Xt represents a chlorine atom and X2 a bromine atom, the compound having the configuration (IR, trans). 2. Compounds according to claim 1, in the form of stereo-isomer A, of stereo-isomer B or of a mixture of these stereo-isomers, the names of which follow: - (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromo-ethyl) cyclopropane-l-carboxylate of (S) a-cyano 3-phenoxybenzyl, - (1R, eis) 2,2-dimethyl 3- (2 ', 2'-dibromo r, 2'-dichloroethyl) -cyclopropane-l-carboxylate of (S) a-cyano 3-phenoxybenzyl, - 3,4,5,6-tetrahydrophthalimido-methyl (IR, trans) 2,2-dimethyl 3- (r, 2 ', 2', 2'-tetrabromoethyl) -cyclopropane-l-carboxylate, - 3,4,5,6-tetrahydrophthalimidomethyl (IR, eis) 2,2-dimethyl 3- (r, 2 ', 2', 2'-tetrabromoethyl) cyclo-propane-l-carboxylate, - (IR, eis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclo-propane-1-carboxylate of (S) a-cyano 3-phenoxybenzyl, - (R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromo-ethyl) cyclopropane-l-carboxylate from (R) a-cyano 3-phenoxybenzyl. 3. The (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromo-ethyl) cyclopropane-l-carboxylate of (S) a-cyano 3-phenoxybenzyl in the form stereo-isomer A, stereo-isomer B or a mixture of these stereoisomers, as a compound according to claim 1. 4. Compounds according to one of claims 1 to 3, in the form of a mixture of stereoisomers of structure eis and structure trans in any proportions, in particular in the weight proportions 20:80, 50:50 or 80:20. 5. Process for the preparation of the compounds of formula (I) according to claim 1, characterized in that an ester of formula is reacted: CH .COOR / 1 in which X1 and R represent the substituents of the compounds of claim 1, with an agent capable of fixing X2, defined as in claim 1, on the double bond of the side chain. 6. Process for preparing the compounds of formula (I) according to claim 1, characterized in that an acid of formula is reacted: in which Xt and R represent the substituents of the compounds of claim 1, with an agent capable of fixing X2, defined as in claim 1, on the double bond of the side chain, then reacting the acid obtained, of formula : OOH • CH. X "2 as such or in the form of a functional derivative, with an alcohol ROH or one of its functional derivatives, R representing the substituent of the compounds of claim 1. 7. Insecticidal composition, characterized in that it contains, as active principle, at least one of the compounds according to claim 1 and an inert support material. 8. Composition according to claim 7, characterized in that it also contains a synergistic agent for pyrethroids. 9. Composition according to claim 8, characterized in that the synergizing agent is piperonyl butoxide. 10. Composition according to one of claims 7 to 9, characterized in that the active principle is (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro l', 2'-dibromoethyl) cyclopropane-1-carboxylate of (S) a-cyano 3-phenoxybenzyl in the form of a stereoisomer A, of stereoisomer B or of a mixture of these stereoisomers. 11. acaricidal composition, characterized in that it contains, as active principle, at least one of the compounds according to claim 1. 12. acaricidal composition according to claim 11 for veterinary use, intended for combating affections caused by mites. 13. Composition according to claim 12, characterized in that it also contains a pyrethroid synergizing agent. 14. Nematicidal composition, characterized in that it contains, as active principle, at least one of the compounds according to claim 1. The compounds of general formula have been described in Swiss Patent No. 630884, in all their possible isomeric forms: , COOR ■ CE X 2 dans'laquelle Xu X2 and X3 represent in particular a fluorine, chlorine or bromine atom and R represents in particular: 5 10 15 20 25 30 35 40 45 50 55 60 65 3 638,179 - a benzyl radical, optionally substituted, - a 5-benzyl 3-furylmethyl group or related groups, - a 2-methyl 3-alkyl 4-oxocyclopent-2-enyl group or related groups, - 3-phenoxybenzyl, a-cyano 3-phenoxy-benzyl or a-ethynyl 3-phenoxybenzyl groups or related groups, - A 3,4,5,6-tetrahydrophthalimidomethyl group or one of the related groups. It has also been indicated that the esters of formula I can exist in many isomeric forms. In fact, the cyclopropanecarboxylic acids forming the acidic copula of the esters of formula I generally have 3 asymmetric carbons, namely, the asymmetric carbons in positions 1 and 3 of the cyclopropane cycle and the asymmetric carbon in position l of the polyhalogenated ethyl side chain attached in position 3. It has also been indicated that the alcohol ROH constituting the alcoholic copula of the esters of formula I may contain one or more asymmetric carbons and / or one or more double bonds giving rise to an E / Z isomerism. It was also pointed out that, in the case where the substituents and X2 are identical, for a determined steric configuration of the asymmetric carbons in positions 1 and 3 of the cyclopropane ring and, for a unambiguous stereochemical structure of the alcoholic part, there may exist two forms diastereoisomers of the esters (I) or of the corresponding acids, due to the existence of the asymmetric carbon at 1 '. These isomers can, in general, be separated and isolated in the pure state; they are called here, and in what follows, isomers (A) and (B).