CH626320A5 - Process for the preparation of esters of cyclopropanecarboxylic acids and of optically active allethrolone, their use and insecticidal composition containing them - Google Patents

Description

The present invention firstly relates to a process for the preparation of esters of cyclopropanecarboxylic acids and of optically active allethrolone from allethrolone sulfonates of antipodal configuration, said esters exerting an insecticidal action and being derived from cyclopropane acids / carboxylic (A), racemic or optically active, of IR, 3R configurations; IS, 3S; IR, 3S; IS, 3R, and optically active allethrolone, of configuration (S) or (R), of general formula:

H3C \

(Sour)

in which either Ri and R2, which are identical or different, represent alkyl radicals comprising from 1 to 3 carbon atoms, or Rx and R2 represent fluorine, chlorine or bromine atoms, or Rx represents an alkyl radical comprising 1 or 2 carbon atoms and R2 represents a radical:

or a radical:

-CH2-0-CH3

either Ri and R2 represent together, with the carbon atom to which they are linked, a carbon homocycle comprising from 3 to 6 carbon atoms, or R! and R2 together represent, with the carbon atom to which they are linked, a cycle of formula:

in which X represents an oxygen or sulfur atom, characterized in that an optically active allethrolone sulfonate of configuration (in an organic solvent or a mixture of organic solvents) is reacted R) or (S), of general formula:

in which X 'represents either an alkyl radical containing from 1 to 3 carbon atoms, or a phenyl radical optionally substituted in the para position by a methyl radical or by a fluorine, chlorine or bromine atom and in which the allethrolone is optically active, of configuration (R) or (S), with a racemic or optically active salt of cyclopropanecarboxylic acid (A), of general formula: n

H

3

H

3

in which R 1 and R 2 retain the abovementioned meanings, in order to obtain the ester of cyclopropanecarboxylic acid (A) and of optically active allethrolone of configuration (S) or (R) antipodal to that of the starting sulfonate.

This process is called process a.

The cyclopropanecarboxylic acid salt (A), used in the process of the invention, is preferably chosen from the group consisting of alkali salts, alkaline earth salts, tertiary base salts and the salt of ammonium.

It is particularly advantageous to use as the salt of cyclopropanecarboxylic acid (A) an alkaline salt.

According to a preferred procedure of the process of the invention, the salt of cyclopropanecarboxylic acid (A) is the sodium salt or the potassium salt.

Among the acids to which the process of the invention applies, there may be mentioned in particular 2,2-dimethyl 3- (2'-methyl l'-propenyl) -cyclopropane 1-carboxylic acids, 2,2-dimethyl 3 acids - (2,2-dichlorovinyl) cyclopropane 1-carboxylic, 2,2-dimethyl 3- (2,2-dibromovinyl) cyclopropane 1-carboxylic acids, 2,2-dimethyl 3- (2,2-difluorovinyl) acids 1-carboxylic cyclopropane, 2,2-dimethyl 3- (2'-methyl 3'-methoxy l '- (E) -propenyl) cyclopropane 1-carboxylic acids, 2,2-dimethyl 3- (2'- ethyl 3'-oxo l'-butényl) cyclopropane 1-carboxylic, 2,2-dimethyl 3- (cyclopentylidenemethyl) cyclopropane 1-carboxylic, 2,2-dimethyl 3- (2'-oxo 3'-oxacyclo -pentylidenemethyl) 1-carboxylic cyclopropane, 2,2-di-methyl 3- (2'-oxo 3'-thiacyclopentylidenemethyl) cyclopropane 1-carboxylic acids, the abovementioned acids possibly being racemic or optically active and, more especially, the acids used in the examples of the experimental part.

The organic solvent, or the mixture of organic solvents, in which the condensation of the allethrolone sulfonate and the salt of cyclopropanecarboxylic acid (A) is carried out, according to the invention,

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is preferably chosen from the group consisting of dimethylformamide, hexamethylphosphorotriamide, dimethylsulfoxide, dimethoxyethane, acetonitrile, aliphatic ketones containing from 3 to 6 carbon atoms, alkanols, monocyclic aromatic hydrocarbons, or by a mixture of these solvents.

According to preferred embodiments of the process of the invention, this solvent is hexamethylphosphorotriamide, dimethylsulfoxide and dimethylformamide.

It is advantageous to use, as a mixture of solvents, a mixture of toluene and dimethyl sulfoxide.

According to other preferred embodiments of the process of the invention, the mixture of solvents used in the process of the invention is a mixture of toluene and secondary or tertiary alkanol comprising from 4 to 6 carbon atoms and, more specifically, a mixture of toluene and tertiary butanol.

The optically active allethrolone sulfonates of general formula II, used at the start of the process of the invention, are described in the French patent application, filed on June 23, 1976 under the number 76-19087 and entitled Optically active allethrolone sulfonates , their preparation process and their application to the inversion of the allethrolone asymmetry center.

These sulfonates can be prepared by reacting, in an organic solvent or a mixture of organic solvents, in the presence of a basic agent, the sulfonic acid chloride of general formula IV:

X'S02C1 (IV)

in which X 'retains the abovementioned meaning, that is to say represents an alkyl radical comprising from 1 to 3 carbon atoms, such as methyl, ethyl, propyl or isopropyl, a phenyl radical optionally substituted in para by a methyl radical or by a fluorine, chlorine or bromine atom, with the optically active allethrolone, of configuration (R) or (S).

The basic agent in which this condensation is carried out is preferably a tertiary base and, in particular, triethylamine.

The organic solvent, or the mixture of organic solvents, used to carry out this condensation is preferably chosen from the group consisting of aliphatic ketones containing from 3 to 6 carbon atoms, monocyclic aromatic hydrocarbons, etheroxides, chlorinated solvents .

Advantageous procedures consist in using as solvent either acetone or toluene.

The sulfonic acid chlorides IV used are preferably methanesulfonyl chloride or paratoluenesulfonyl chloride.

Examples of the preparation of optically active allethrolone sulfonate are given later in the experimental part.

According to an advantageous embodiment of the process of the invention, allethrolone sulfonate is used in solution without isolating it from the reaction medium in which it has been formed.

Then preferably used as a solvent to prepare the optically active allethrolone sulfonate, a monocyclic aromatic hydrocarbon.

The salt of cyclopropanecarboxylic acid is prepared according to known methods, by the action of the acid on the corresponding base in an organic solvent.

According to a preferred procedure of the invention, the salt of cyclopropanecarboxylic acid in solution is used, without isolating it from the reaction medium in which it has been formed.

Then preferably used for the preparation of the cyclopropanecarboxylic acid salt (A), a solvent or a mixture of solvents chosen from the group consisting of dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide, dimethoxyethane, acetonitrile, aliphatic ketones containing from 3 to 6 carbon atoms, alkanols, monocyclic aromatic hydrocarbons, or by a mixture of these solvents.

The process of the invention applies, in particular, to the case where the cyclopropanecarboxylic acid (A) is 2,2-dimethyl 3R- (2'-methyl 1 '-propenyl) cyclopropane IR-carboxylic acid, the acid

2,2-dimethyl 3S- (2'-methyl l'-propenyl) cyclopropane 1 R-carboxylic acid 2,2-dimethyl 3R- (cyclopentylidenemethyl) -cyclopropane IR-carboxylic acid (1 R, trans ) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) 1-carboxylic cyclopropane, acid (IR, trans) 2,2-dimethyl 3- (2', 2'-difIuorovinyl) cyclopropane 1-carboxylic , (1R, cis) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) -cyclopropane 1-carboxylic acid.

It is known that, in general, the esters of cyclopropanecarboxylic acids and of optically active allethrolone, of configuration (S), have an insecticidal activity much higher than that of the esters of cyclopropanecarboxylic acids and of allethrolone, (R), or racemic, configuration (R, S). On this subject, see “Fortschritte der Chemie organischer Naturstoffe”, 19 (1961), p. 120 et seq.

To prepare the esters of cyclopropanecarboxylic acids of optically active allethrolone of configuration (S), the only method known to date consisted of esterifying a cyclopropanecarboxylic acid or one of its functional derivatives with optically active allethrolone of configuration (S). The optically active allethrolone of configuration (S) has long been inaccessible on an industrial scale. There are now processes for splitting the racemic allethrolone (R, S) making it possible to obtain the allethrolone of configuration (S) (cf. French patent No. 2166503) with weight yields which obviously cannot exceed 50% compared to starting racemic allethrolone.

The optically active allethrolone of configuration (R), originating from this duplication, therefore constitutes a product without practical utility, and it is of great industrial interest to be able to revalue this allethrolone of configuration (R).

The process which is the subject of the present invention provides a particularly advantageous solution to this important industrial problem. Indeed, it makes it possible, in a single simple reaction step, to obtain directly, from allethrolone of configuration (R), the esters of cyclopropanecarboxylic acids of configuration (S) with a high yield.

It has the advantage, over the already existing processes, of not leading intermediately to an allethrolone of configuration (S) isolated, which must then be esterified with suitable cyclopropanecarboxylic acid (which must first be transformed into acid chloride).

The process of the invention is obviously of particular interest when the starting allethrolone is the allethrolone of configuration (R).

Furthermore, the processes for splitting allethrolone are not quantitative and in practice provide, alongside the allethrolone of configuration (S) desired, a mixture of allethrolone of configuration (R) and of allethrolone of configuration ( S) rich in allethrolone of configuration (R).

After transformation of these mixtures into sulfonate, a mixture of allethrolone sulfonate of configuration (R) and of allethrolone sulfonate of configuration (S) rich in allethrolone of configuration (R) is obtained.

The process of the invention applies to these mixtures.

The subject of the invention is therefore a process in accordance with general process a, in which the starting optically active allethrolone sulfonate consists of a mixture of allethrolone sulfonate of configuration (S) and of allethrolone sulfonate of configuration ( R) rich in sulfonate of configuration (R).

The process of the invention has an unexpected character. Although some examples of reversal of optically active aliphatic alcohols are already known, by the action of an acetate on the alcohol tosylate, the reversal of the center of asymmetry of allethrolone, although exhibiting great industrial importance, had never been achieved using this type of process.

The success of such a reversal process in the case of allethrolone was, in fact, a priori very difficult, especially because access to

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allethrolone sulfonates presents barriers. It is thus known that by treating alletrholone with methanesulfonyl chloride in the presence of a weak base such as pyridine, the chlorine derivative is obtained and not the sulfonate.

Allethrolone sulfonates, as described in the invention, are fragile products, sensitive to heat and to the presence of mineral or organic bases which cause them to lose the sulfonyl group and lead to doubly Diels Aide's reaction.

O

These sulfonates are also sensitive to the presence of basic hydrochlorides, such as triethylamine hydrochloride which induces the formation of the chlorinated derivative.

The preparation of the allethrolone sulfonates described in the invention therefore requires that the difficulties listed be resolved by suitable solutions, that is to say that the reaction is carried out at low temperature under conditions of limited alkalinity. , that a reaction solvent is used, in which the insoluble triethylamine hydrochloride formed during the sulfonation, which makes it unfit to react quickly on allethrolone sulfonate.

The reaction of allethrolone sulfonate with a salt of cyclopropane carboxylic acid also presents risks of several kinds:

On the one hand, the evolution of the sulfonate towards the formation of doubling products as a result of the alkalinity provided by the salt of cyclopropanecarboxylic acid,

- on the other hand, an incomplete epimerization which would lead to a partial racemization of the center of asymmetry of allethrolone.

The process of the invention makes it possible to remarkably reduce the dreaded side reactions and leads, in very high yields (both chemically and optically) to pure products.

The process of the present invention makes it possible to obtain, as new industrial products:

- 2,2-dimethyl 3R- (cyclopentylidenemethyl) cyclopropane 1R-carboxylate of (S) allethrolone,

- 2,2-dimethyl 3S- (2 ', 2'-dichlorovinyl) cyclopropane lR-carboxylate of (S) allethrolone or (IR, trans) 2,2-dimethyl 3- (2', 2'-dichlorovinyl) cyclopropane (S) allethrolone 1-carboxylate,

- 2,2-dimethyl 3S- (2 ', 2'-difluorovinyl) cyclopropane lR-carboxylate of (S) allethrolone or (IR, trans) 2,2-dimethyl 3- (2', 2'-difluorovinyl) cyclopropane (S) allethrolone 1-carboxylate and 2,2-dimethyl 3R- (2 ', 2'-difhiorovinyl) cyclopropane 1R (S) allethrolone or (lR, cis) 2,2-dimethyl 3- (2) carboxylate ', 2'-difluorovinyl) cyclopropane 1-carboxylate of (S) allethrolone.

These four new products have a significant insecticidal activity which allows their use, according to a second object of the invention, as insecticidal agents. This activity has been demonstrated in a study given below.

Thus, these products prove to be endowed with an extremely high knock-down power (or power for slaughtering insects), while possessing a good lethal activity.

They find, in particular, their use in the domestic field. They can also be used in the agricultural field. In the latter case, in particular, they can be used in combination with other pyrethroid compounds.

The insecticidal activity of these products could, for example, be demonstrated by knock-down activity tests or by lethal activity tests on house flies, as well as by tests on Aedes aegypti. In the latter case, they were used by incorporating them into fumigant compositions.

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The four new products mentioned above can be used to prepare insecticide compositions containing, as active principle, at least one of said products; these compositions also constitute an object of the invention.

The above four products can advantageously be used in combination with a synergistic agent such as piperonyl butoxide or N- (2-ethylheptyl) -bicyclo- (2,2, 1) -5-hepten-2, 3-dicarboxiimide.

The active ingredient (s) can optionally be added with one or more other pesticidal agents. These compositions may 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 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 pyrethrum marc.

These insecticidal compositions preferably contain from 0.01 to 40% by weight of active ingredient.

The use of the four products mentioned above in the form of fumigant compositions is particularly advantageous.

These compositions can be constituted in particular by an insecticidal coil preferably containing from 0.01 to 10% by weight 45 of at least one of the four products mentioned above, as active ingredient, and by an inert combustible support composed for example pyrethrum marc, Tabu powder (or Machilus thumbergii leaf powder), pyrethrum stem powder, cedar leaf powder, wood powder (such as sawdust), starch and walnut shell powder coconut.

They can also be obtained by incorporating at least one of the four products preferably at a concentration of 0.01 to 95% by weight in an incombustible fibrous substrate and by placing the fumigant thus obtained on a heating device, for example a device called 55 usually Electro mosquito destroyer, intended to vaporize the active component, thus giving rise to a vaporization which can be extended at will.

One can also, to obtain such a composition, prepare a sprayable oil preferably containing from 0.01 to 95% by weight 60 of at least one of said products. This oil can soak the wick of a lamp and be subjected to combustion, which also has the effect of vaporizing the active ingredient.

2,2-Dimethyl 3S- (2 ', 2'-difluorovinyl) cyclopropane 1R (S) allethrolone or (IR, trans) 2,2-dimethyl 65 3- (2', 2'-difluorovinyl) cyclopropane (S) allethrolone 1-carboxylate and 2,2-dimethyl 3R- (2 ', 2'-difluorovinyl) cyclopropane 1R (S) allethrolone or (1R.cis) 2,2-dimethyl 3- cyclo-boxylate (2 ', 2'-di-fluorovinyl) cyclopropane 1-carboxylate of (S) allethrolone possè

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dent a particularly interesting activity when used in the form of fumigant compositions.

The following examples illustrate the invention.

Example 1:

2,2-Dimethyl3R- (2'-methyl l'-propenyl) cyclopropane 1 R-carboxylate of 2-allyl 3-methyl 4R-hydroxy 2-cyclopent-l-one or d-transchrysanthemate of (R) allethrolone from (S) allethrolone methanesulfonate.

12.5 g of (S) allethrolone methanesulfonate are added to 33 cm 3 of hexamethylphosphorotriamide, 9.65 g of sodium salt of d-transchrysanthemic acid are added, the mixture is stirred for 10 min, a mixture of normal soda is added, of water and n-heptane, stirred, separates the organic phase by decantation, extracts the aqueous phase with heptane, combines the organic phases, washing them, drying them, and obtains 12.94 g of d-transchrysanthemate from ( R) allethrolone.

Circular dichroism (dioxane)

Infi.

345 nm

Ae =

- 1.18

Max.

332 nm

Ae =

- 2.41

Max.

321 nm

Ae =

- 2.73

Infi.

310 nm

Ae =

- 2.08

Max.

230 nm

Ae =

+ 15.9

The (S) allethrolone methanesulfonate used can be prepared in the following manner.

7.35 g of (S) allethrolone are dissolved in 7.5 cm3 of acetone, cooled to -15 ° C., 8.4 cm3 of triethylamine are added, then 4.3 cm3 of methanesulfonyl chloride dissolved in 11 cm3 is added slowly of acetone, stirred for 15 min, pour the reaction mixture into a mixture of 23 cm3 of normal hydrochloric acid, 56 cm3 of water and 23 cm3 of methylene chloride, stirred for 15 min, separates the phase by decantation organic, extract the aqueous phase with methylene chloride, combine the organic phases, wash them, dry them, concentrate them to dryness, and obtain 12.5 g of crude (S) allethrolone methanesulfonate used as it is for the condensation of example 1.

The sodium salt of chrysanthemic acid, used in Example 1, can be prepared as follows.

In a solution of 16.8 g of 2,2-dimethyl 3R- (2'-methyl l'-propenyl) cyclopropane 1R-carboxylic acid in 50 cm3 of acetone, the required amount of aqueous ION sodium hydroxide solution is introduced to obtain the change in phenolphthalein, isolate by wringing the precipitate formed, wash it, dry it, and obtain 18.6 g of sodium salt of 2,2-dimethyl 3R- (2'-methyl l'- propenyl) cyclopropane 1 R-carboxylic acid used as such for the condensation of Example 1.

Example 2:

2,2-Dimethyl 3R- (2 '-methyl l'-propenyl) cyclopropane 1 (S) allethrolone R-carboxylate from (R) allethrolone methanesulfonate.

By following a procedure analogous to that of Example 1 starting from (R) allethrolone methanesulfonate, 2,2-dimethyl 3R- (2'-methyl 1'-propenyl) cyclopropane 1 R- is obtained with the same yield. (S) allethrolone carboxylate; [a] ^ § = - 50 ° (c = 5%, toluene).

Example 3:

2,2-Dimethyl 3R- (2 '-methyl l'-propenyl) cyclopropane 1 (R) allethrolone R-carboxylate from (S) allethrolone methanesulfonate.

To the potassium salt solution obtained below starting from 110 g of d-transchrysanthemic acid, a solution of 165 g of (S) allethrolone methanesulfonate in 350 cm3 of dimethyl sulfoxide, stirred, is quickly added at + 15 ° C. for 24 h at 20 ° C, add 100 cm3 of heptane, 500 cm3 of water, stir, separate the organic phase by decantation, extract the aqueous phase with heptane, join the heptane phases, wash them with an aqueous solution N of sodium hydroxide, then with water, extracts the aqueous washes with heptane, combines the heptane fractions, dries them, concentrates them dry by distillation, and obtains

169 g of 2,2-dimethyl 3R- (2'-methyl l'-propenyl) cyclopropane 1 R-carboxylate of (R) allethrolone; [a] ^ = + 11 ° (c = 1%, ethanol).

UV spectrum (ethanol)

5 Maximum at 225 nm, E} = 600; maximum at 295 nm, EJ = 3.

Circular dichroism (dioxane)

Max.

230 nm

Ae =

+ 15

Infi.

310 nm

Ae =

- 2.15

Max.

320 nm

Ae =

- 2.70

Infi.

330 nm

Ae =

- 2.43

Infi.

345 nm

Ae =

- 1.14

The (S) allethrolone methanesulfonate, used starting from Example 3, can be prepared in the following manner.

In 200 cm3 of acetone, 100 g of (S) allethrolone are dissolved; Eb.0i6mm / Hg = 115 ° C; [a] $ = + 14 ° (c = 1.3%, chloroform), UV absorption (ethanol): maximum at 229 nm, E} = 810; 114.5 cm3 of triethylamine are added at -15 ° C., stirred, introduced between 0 and + 5 ° C., a solution of 86.5 g of methanesulfonyl chloride in 180 cm3 of anhydrous acetone, in approximately 20 minutes, stirred for 20 min at -10 ° C, introduced at - 15 ° C 200 cm3 of methylene chloride, then a mixture of 50 cm3 of 11.8N aqueous hydrochloric acid solution, stirred, separates the organic phase by decantation, extracts the aqueous phase with methylene chloride, joins the organic phases, washing them with water, extracts the aqueous washes with methylene chloride, joins the chloromethylenic solutions, washing them, drying them, concentrating them to dryness under reduced pressure, and obtains 165 g of crude (S) allethrolone methanesulfonate, used as it is for the condensation 3o of Example 3 with the potassium salt of d-transchrysanthemic acid.

The potassium salt solution of d-trans-chrysanthememic acid, used in Example 3, can be prepared as follows.

35 In a mixture of 100 cm3 of dimethyl sulfoxide and 30 cm3 of water, 110 g of 2,2-dimethyl 3R- (2'-methyl 1'-propenyl) cyclopropane 1 R-carboxylic acid, [a] ^ are introduced. = + 36.7 ° (dimethylformamide), add at 4-15 ° C the necessary quantity of aqueous potassium hydroxide solution at 50 ° B, to obtain the pink turn of 40 phenolphthalein (about 49.5 cm3), add 0 , 7 cm3 of water, and obtains a solution containing the potassium salt of 2,2-dimethyl 3R- (2'-methyl l'-propenyl) cyclopropane 1 R-carboxylic acid.

Example 4:

45 2,2-Dimethyl 3R- (2'-methyl l'-propenyl) cyclopropane

1 2-allyl 3-methyl 4S-hydroxy 2-cyclopent-1-one or d-transchrysanthemate (S) allethrolone R-carboxylate starting from (R) allethrolone methanesulfonate.

To the potassium salt solution of d-trans-50 chrysanthememic acid, obtained below from 11 g of d-transchrysanthemic acid, a solution of 16 g of methanesulfonate is added at + 15 ° C. (R) allethrolone in 35 cm3 of dimethylsulfoxide, stirred for 24 h at 20 ° C, added water, heptane, stirred, separated by decantation the organic phase; the aqueous phase is re-extracted with 55 heptane, the organic phases are joined, washed with N sodium hydroxide, then with water, dried, concentrated to dryness and 16.1 g of 2,2-dimethyl 3R are obtained - (2'-methyl l'-propenyl) cyclopropane 1 (S) allethrolone R-carboxylate.

60 UV spectrum (ethanol)

Max. 227-228 nm e = 17400

We deduce a chemical purity in allethrolone chrysanthemate of 94%.

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Circular dichroism (dioxane)

Max. 227.5 nm Ae = - 24.5 Infi. 310 nm A "= - 1.87

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Max. 320 nm Ae = - 2.40 Max. 332 nm Ae = - 2.16 Infi. 345 nm Ae = - 1.02

This dichroism corresponds to 90% ester of (S) allethrolone,

4% (R) allethrolone ester,

plus 6% of impurities (according to UV titer) not affecting the DC.

90

The optical purity of the ester is therefore # 95.8%.

90 + 4

The rate of stereoconversion (R) allethrolone- »ester of (S)

(95.8)

allethrolone is therefore quantitative

95.5

The (R) allethrolone methanesulfonate, used starting from Example 4, can be prepared in the following manner.

An (R) allethrolone of [a] ^ = —15 ° + 1 ° (c = 1%, chloroform) is used which, according to its circular dichroism, contains 95.5% of (R) isomer and 4 , 5% isomer (S).

10 g of (R) allethrolone are dissolved in 20 cm 3 of acetone, cooled to -15 ° C., 11.4 cm 3 of triethylamine are added, then, while maintaining the temperature below 0 ° C., a mixture of 18 cm 3 of acetone and 5.8 cm 3 of methanesulfonyl chloride, stirred for 20 min at -10 ° C., introduced methylene chloride,

acidifies by addition of an aqueous solution of hydrochloric acid N, agitates, separates the organic phase by decantation, again extracts the aqueous phase with methylene chloride, joins the chloromethylenic phases, washing them with water, drying them, concentrated under reduced pressure, and obtains 16 g of (R) allethrolone burt methanesulfonate used as it is for Example 4.

The potassium salt solution of d-transchrysanthemic acid, used in Example 4, can be prepared as follows.

11 g of d-transchrysanthemic acid (1R, 3R) are dissolved in 10 cm 3 of dimethyl sulphoxide, 3 cm 3 of water, a drop of alcoholic solution of phenolphthalein, added with potassium hydroxide solution, until the phenolphthalein turns.

Example 5:

2,2-Dimethyl 3R- (2'-methyl l'-propenyl) cyclopropane

1 (S) allethrolone R-carboxylate from (R) allethrolone methanesulfonate (without isolation of the intermediate methanesulfonate).

At 20 ° C., the (R) allethrolone methanesulfonate solution obtained below is rapidly introduced starting from 250 g of (R) allethrolone in the potassium salt solution of d-transchrysanthemic acid obtained below at departure of 293 g of d-transchrysanthememic acid, stirred for 24 h at 20 ° C, added, in about 10 minutes at 20 ° C 750 cm3 of water, stirred, separated by decantation the organic phase, extracted the aqueous phase with toluene, wash the combined organic phases with water using an aqueous N sodium hydroxide solution, with water, dry over magnesium sulfate, filter, add 250 g of alumina, stir, filter, concentrate to dryness under reduced pressure, and obtains 400.7 g of 2,2-dimethyl 3R- (2'-methyl-1-propenyl) cyclopropane 1 R-carboxylate of (S) allethrolone; [a] ^ § = —49 ° (c = 5%, toluene).

The (R) allethrolone methanesulfonate solution used starting from Example 5 is prepared as follows.

250 g of (R) allethrolone, [a] ^? = —10.5 ° (c = 10%, chloroform), are dissolved in 750 cm3 of toluene, introduced in about 10 minutes at

- 13 ° C 225 g of methane sulfonyl chloride, then in about 2 hours at

- 8 ° C a solution of 217.5 g of triethylamine in 200 cm3 of toluene, stirred for 15 min, added at -5 ° C in 30 min about 1000 cm3 of water, stirred, separated by decantation of the organic phase, extracted the toluene aqueous phase, combines the toluene phases, washes them with water, extracts the aqueous toluene washes, combines the toluene solutions, dries them, and obtains a toluene solution of (R) allethrolone methane sulfonate used as it is for Example 5.

The potassium salt solution of d-transchrysanthemic acid, used in Example 5, can be prepared as follows.

In 500 cm3 of dimethyl sulfoxide, 293 g of 2,2-dimethyl 3R- (2'-methyl l'-propenyl) cyclopropane 1R-carboxylic acid, dissolved at 40 ° C. are dissolved in approximately 184.2 g of aqueous potassium hydroxide solution at 50 ° B, stirred for 30 min at 40 ° C, and obtains a potassium salt solution of 2,2-dimethyl 3R- (2'-methyl-propenyl) cyclopropane acid 1 R-carboxylic.

Example 6:

2,2-Dimethyl 3 R- (2'-methyl l'-propenyl) cyclopropane 1 (R) allethrolone R-carboxylate from (S) allethrolone methanesulfonate (without isolation of the intermediate methanesulfonate).

Starting from 250 g of (S) allethrolone, [a] ^ $ = + 14 ° (c = 1.3%, chloroform), a toluene solution of (S) allethrolone methanesulfonate is prepared by operating in a similar manner to that of Example 5, and obtains, after condensation with the potassium salt of d-transchrysanthemic acid used in solution according to a procedure analogous to that of Example 5.397 g of 2,2-dimethyl 3R- (2 ' -methyl r-propenyl) cyclopropane 1 R-carboxylate of (R) allethrolone; [a] | J = —4 ° (c = 5%, toluene).

Example 7:

2,2-Dimethyl 3R- (2 '-methyl l'-propenyl) cyclopropane 1 (S) allethrolone R-carboxylate from (R) allethrolone methanesulfonate (without isolation of the intermediate methanesulfonate).

In the potassium d-transchrysanthemate solution obtained below starting from 82.8 g of d-transchrysanthemic acid, the (R) allethrolone methanesulfonate solution obtained below is introduced at 18-20 ° C. in a few minutes after leaving 50 g of (R) allethrolone, vigorously agitated for 35 h at 18-20 ° C, adds 150 cm3 of water, separates the toluene phase by decantation, extracts the aqueous phase with toluene, combines the toluene phases, wash them with water, join the toluene phases, wash them until the absence of chrysanthemic acid using an aqueous solution containing 5% sodium bicarbonate and 5% sodium carbonate, then with water until neutrality, dry, filter, add 0.1 g of hydroqui-none to the filtrate, concentrate to dryness by distillation under reduced pressure, and obtain 92.9 g of 2,2-dimethyl 3R- (2'-methyl l'- propenyl) cyclopropane

1 (S) allethrolone R-carboxylate; [<x] ^ § = —50.5 ° 9c = 5%, toluene).

The (R) allethrolone methanesulfonate solution, used in Example 7, is prepared as follows.

In 150 cm3 of toluene, 50 g of (R) allethrolone are introduced and then, in approximately 10 minutes at 0 ° C, 45 g of methanesulfonyl chloride, then a solution of 43.5 g is added in approximately 1 hour at 0 ° C of triethylamine in 40 cm3 of toluene, stirred for 30 min at 0 ° C, introduced at 01C in 30 min about 200 cm3 of water, stirred, separated by decantation of the toluene phase, washed with water until no chloride, operating at a temperature below +51 C, dries the toluene solution, filters, and obtains a solution of (R) allethrolone methanesulfonate used as it is in Example 7 for condensation with the potassium salt of chrysanthemic acid.

The potassium salt solution of d-transchrysanthemic acid, used in Example 7, can be prepared as follows.

In a mixture of 100 cm3 of tertiary butanol and 100 cm3 of toluene, 24.9 g of potash containing 90.8% are introduced at 20 ° C., added in approximately 30 minutes at 25-30 ° C 82.8 g of 2,2-dimethyl 3R- (2'-methyl l'-propenyl) cyclopropane 1 R-carboxylic acid, stirred for

2 'A h at 25-30 ° C, cools to 20 ° C, and obtains a potassium salt solution of 2,2-dimethyl 3R- (2'-methyl l'-propenyl) cyclo-propane 1 R-carboxylic acid used as such for Example 7.

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626,320

Example 8

2,2-Dimethyl 3S- (2'-methyl l'-propenyl) cyclopropane 1 (S) allethrolone R-carboxylate from (R) allethrolone methanesulfonate (without isolation of the intermediate methanesulfonate).

10 g of the sodium salt of 2,2-dimethyl 3S- (2'-methyl 1'-propenyl) cyclopropane 1 R-carboxylic acid are introduced into a mixture of 20 cm 3 of toluene and 20 cm 3 of terbutanol then quickly 31.8 cm3 of toluene solution at 1.1 mol / 1 of (R) allethrolone methanesulfonate, stirred for 2 h, added 30 cm3 of terbutanol, stirred for 65 h, added water, extracted with ether, wash the ethereal extracts with water with a dilute aqueous ammonia solution, with water, dry, concentrated to dryness by distillation under reduced pressure, and obtain 9.94 g of crude ester which is purified by chromatography on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (9/1) and obtaining 7.38 g of 2,2-dimethyl 3S- (2'-methyl 1 '-propenyl) cycopropane 1 (S) allethrolone R-carboxylate; [œ] ^ = + 39.5 ° (c = 0.8%, chloroform).

Circular dichroism (dioxane)

Ae = —9.85 at 231 nm Ae = + 2.68 at 320 nm Ae = +2.38 at 332 nm

The sodium salt of cischrysanthemic acid, used in Example 8, is prepared as follows.

20 g of ethanol are introduced into 20 g of 2,2-dimethyl 3S- (2'-methyl l'-propenyl) cyclopropane 1 R-carboxylic acid, a few phenolphthalein crystals, slowly adding concentrated sodium hydroxide solution until turning pink, remove the solvents by distillation under reduced pressure, and obtain 22 g of sodium salt of 2,2-dimethyl 3S- (2'-methyl 1 '-propenyl) cyclopropane 1 R-carboxylic acid .

The toluene solution of (R) allethrolone methanesulfonate, used in Example 8, is prepared in the following manner.

35 g of freshly rectified (R) allethrolone are introduced into 105 cm 3 of toluene (bp = 97 ° C. under 0.2 mm Hg), stirred,

cooled to + 2 "C, added in 15 min at + 2 ° C 22 cm3 of methanesulfonyl chloride, introduced in 1 h at + 2 ° C a mixture of 28 cm3 of toluene and 42 cm3 of triethylamine, stirred for 30 min at 0 ° C, add in 10 min at 0 C 35 cm3 of ice water, then 100 cm3 of ice water in one go, stir, separate the aqueous phase from the organic phase by decanting, wash the organic phase with water at 0 ° C, dry the toluene phase, filter and store the solution obtained at 0 ° C. This solution contains 1.13 mol of allethrolone methanesulfonate per liter.

Example 9:

2,2-Dimethyl 3S- (2'-methyl l'-propenyl) cyclopropane 1 (S) allethrolone R-carboxylate from (R) allethrolone paratoluene sulfonate.

2.28 g of sodium salt of 2,2-dimethyl 3S- (2'-methyl l'-propenyl) cyclopropane 1 R are introduced into a mixture of 20 cm3 of dimethyl sulfoxide and 2 cm3 of water -carboxylic, then 3.4 g of (R) allethrolone paratoluene sulfonate, stirred for 2 h at room temperature, poured into an aqueous solution of hydrochloric acid, stirred, extracted the aqueous phase with petroleum ether (Eb. 35-75 JC), wash the organic extracts with water, dry, concentrate to dryness, 3.4 g of residue is obtained which is chromatographed on silica gel, eluting with a mixture of benzene and acetate ethyl (9/1), and collects 2.06 g of 2,2-dimethyl 3S- (2'-methyl l'-propenyl) cyclo-propane 1 R-carboxylate of (S) allethrolone.

Circular dichroism (dioxane)

Ae = —7.8 at 233 nm Ae = +2.4 at 320 nm Ae = +2.1 at 332 nm

The sodium salt of cischrysanthemic acid, used in Example 9, is prepared in the same manner as in Example 8.

The (R) allethrolone paratoluenesulfonate, used in Example 9, is prepared in the following manner.

11.6 g of triethylamine are introduced into 100 cm3 of tetrahydrofuran containing 11.6 g of (R) allethrolone under an inert atmosphere, then 21.9 g of paratoluenesulfonyl chloride, stirred for 48 h at + 5 ° C. , pour the reaction mixture into a 0.1N aqueous hydrochloric acid solution, stir, extract the aqueous phase with chloroform, wash the organic extracts with water, dry, concentrate to dryness, chromatograph the residue (29 g) on gel silica by eluting with a mixture of benzene and ethyl acetate (95/5) and obtains 6.8 g of (R) allethrolone paratoluenesulfonate.

Example 10:

2,2-Dimethyl 3S- (2'-methyl l'-propenyl) cyclopropane 1 (S) allethrolone R-carboxylate from (R) allethrolone parabromobenzenesulfonate.

3.8 g of sodium salt of 2,2-dimethyl 3S- (2'-methyl 1'-propenyl) cyclopropane are introduced into a mixture of 38 cm3 of dimethyl sulfoxide and 3.8 cm3 of water 1 R-carboxylic, introduced 3.77 g of (R) allethrolone parabromobenzenesulfonate and 5 cm3 of dimethylsulfoxide, stirred for 30 min, left to stand for 15 h, added an aqueous solution of hydrochloric acid, extracted the aqueous phase to petroleum ether (bp = 35-75 ° C), wash the organic phases with sodium hydroxide N, with water, dry, concentrate to dryness, gives 1.02 g of residue which is chromatographed on gel silica, eluting with a mixture of petroleum ether (bp = 35-75 ° C) / ethyl ether (7/3), and obtains 0.422 g of 2,2-dimethyl 3S- (2'-methyl l ' -propenyl) -cyclopropane 1 (S) allethrolone R-carboxylate.

Circular dichroism (dioxane)

Ae = —3.4 at 233 nm Ae = +1.5 at 321 nm As = +1.7 at 332nm

The sodium salt of cischrysanthemic acid, used in Example 10, is prepared in the same way as that prepared in Example 8.

The (R) allethrolone parabromobenzenesulfonate, used in Example 10, is prepared in the following manner.

2.5 g of (R) allethrolone are introduced into 25 cm 3 of tetrahydrofuran, cooled to 0 ° C., 2.5 g of triethylamine are added, then 6.3 g of parabromobenzenesulfonyl chloride, stirred for 6 h at + 5 ° C, add a dilute aqueous solution of hydrochloric acid, stir, extract with methylene chloride, wash the combined organic phases with water, dry, concentrate to dryness and obtain 7.47 g of crude (R) allethrolone parabromobenzenesulfonate which is used as is for Example 10.

Example 11:

2,2-Dimethyl 3R- (cyclopentylidenemethyl) cyclopropane 1 R-carboxylate of 2-allyl 3-methyl 4S-hydroxy 2-cyclopent-1-one ((S) allethrolone ester) starting from (R) methanesulfonate allethrolone.

0.530 g of (R) allethrolone methanesulfonate obtained below is dissolved starting from 0.362 g of (R) allethrolone in 10 cm 3 of dimethylformamide, cooled to + 5 ° C., 0.576 g of potassium salt obtained below is added to start of 2,2-dimethyl 3R- (cyclo-pentylidenemethyl) 1 R-carboxylic acid, stir at + 5 ° C for 1 h, pour into water, acidify to pH 4 by addition of dilute hydrochloric acid, extract with petroleum ether, dry the organic phase and concentrate, chromatograph the residue on silica gel, eluting with a mixture of benzene and ethyl acetate (95/5), and isolate 0.443 g of 2.2- dimethyl 3R- (cyclopentylidenemethyl) cyclopropane 1 (S) allethrolone R-carboxylate which has the following characteristics: [a] g = - 38 ° ± 2.5 ° (c = 0.6%, chloroform).

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Circular dichroism (dioxane)

Infi.

345 nm

Ae =

- 1.09

Max.

332 nm

Ae =

- 2.32

Max.

320 nm

Ae =

- 2.60

Infi.

310 nm

Ae =

- 1.97

Max.

230 nm

Ae =

+26.7

The (R) allethrolone methanesulfonate, used starting from Example 11, can be prepared in the following manner.

0.362 g of (R) allethrolone (which, according to its circular dichroism, has an optical purity of 97-98%) is dissolved in 4 cm 3 of a mixture of benzene and ether (50/50), cooled to -6 ° C, added 0.46 cm3 of triethylamine, then slowly 0.2 cm3 of methanesulfonyl chloride dissolved in 2.7 cm3 of a mixture of benzene and ether (50/50), stirred for 2 h at -10 ° C, pour into a dilute hydrochloric acid solution, separate the organic phase by decantation, extract the aqueous phase with ether, combine the organic phases, wash them with water, dry them, concentrated to dryness by distillation under reduced pressure, and obtains 0.530 g of crude (R) allethrolone methanesulfonate used as it is for Example 11.

The potassium salt of 2,2-dimethyl 3R- (cyclo-pentylidenemethyl) cyclopropane 1 R-carboxylic acid, used in Example 11, can be prepared in the following manner.

0.576 g of 2,2-dimethyl 3R- (cyclopentylidenemethyl) -cyclopropane 1 potassium R-carboxylate is prepared by neutralization of a methanolic solution of 2,2-dimethyl 3R- (cyclopentylidene-methyl) cyclopropane 1 R-carboxylic acid with methanolic potassium hydroxide (toning of phenolphthalein), dry distillation under reduced pressure and benzene entrainment.

Example 12:

2,2-Dimethyl 3S- (2 ', 2'-dichlorovinyl) cyclopropane 1 (S) allethrolone R-carboxylate or (IR, trans) 2,2-dimethyl 3- (2', 2'-dichlorovinyl) cyclopropane 1 (S) allethrolone carboxylate from (R) allethrolone methanesulfonate (without isolation of the intermediate methanesulfonate).

10 g of the sodium salt of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1 are introduced into a mixture of 20 cm3 of toluene and 20 cm3 of terbutanol -carboxylic, then 26.2 cm3 of toluene solution of (R) allethrolone methanesulfonate titrating 1.3 mol / 1, stirred for 2 h, added 30 cm3 of toluene and 20 cm3 of terbutanol, stirred for 65 h, treated so analogous to that of Example 8, 9.26 g of crude ester is obtained, which is chromatographed on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (9/1), and obtains 7 , 91 g of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1-carboxylate of (S) allethrolone; Mo = 26 ° (c = 0.5%, chloroform).

Circular dichroism (dioxane)

As = —23.6 to 228nm Ae = + 2.62 to 321 nm Ae = + 2.32 to 332 nm

The sodium salt of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1-carboxylic acid, used in Example 12, is obtained in the following manner.

20 g of ethanol are introduced into 20 g of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1-carboxylic acid, a few phenolphthalein crystals, slowly adding detergent of soda until turning pink, concentrated to dryness by distillation under reduced pressure, adds benzene, concentrated to dryness, performs this operation a second time, and obtains 22.6 g of sodium salt of the acid (1 R , trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1-carboxylic.

The toluene solution of (R) allethrolone methanesulfonate, used in Example 12, is prepared in the same manner as that used in Example 8.

626320

Example 13:

2,2-Dimethyl 3 S- (2 ', 2'-dichlorovinyl) cyclopropane 1 (S) allethrolone R-carboxylate or (IR, trans) 2,2-dimethyl 3- (2', 2'-dichlorovinyl) cyclopropane (S) allethrolone 1-carboxylate from (R) paratoluenesulfonate

allethrolone.

2.78 g of sodium salt of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) acid are introduced into a mixture of 20 cm3 of dimethyl sulfoxide and 2 cm3 of water ) 1-carboxylic cyclopropane,

then 3.4 g of (R) allethrolone paratoluenesulfonate, stirred for 2 h at room temperature, acidified, extracted with petroleum ether (bp = 35-75 ° C), washed the organic phases with IN soda, then with water, dried, concentrated to dryness, obtains 3 g of residue which is chromatographed on silica gel, eluting with a mixture of benzene and ethyl acetate (9/1), and obtains 2.31 g of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1-carboxylate from (S) allethrolone.

The sodium salt of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-di-chlorovinyl) cyclopropane 1-carboxylic acid is obtained in the same manner as in Example 12.

The (R) allethrolone paratoluenesulfonate used in Example 13 is obtained like that of Example 9.

Example 14:

2,2-Dimethyl 3S- (2 ', 2'-difluorovinyl) cyclopropane 1 (S) allethrolone or (IR, trans) R-carboxylate 2,2-dimethyl 3- (2', 2'-difluorovinyl) cyclopropane 1 (S) allethrolone carboxylate from (R) allethrolone methanesulfonate (without isolation of the intermediate methanesulfonate).

18.26 g of sodium salt of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) acid are introduced into a mixture of 36 cm3 of toluene and 36 cm3 of terbutanol 1-carboxylic cyclopropane, added in 1 minute 54.5 cm3 of toluene solution of (R) allethrolone methanesulfonate titrating 1.13 mol / 1, stirred for 76 h at 20 ° C, treated in an identical manner to that of the example 8, obtains 18.69 g of ester or chromatograph on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (9/1), and obtains 15.1 g of (IR, trans) (S) allethrolone 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylate; [a] | J = —24.5 ° (c = 1%, chloroform).

Circular dichroism (dioxane)

As = - 22.6 at 225 nm As = + 2.51 at 320 nm Ae = + 2.23 at 332 nm

UV spectrum (ethanol)

Max. at 228 nm e = 15300

The sodium salt, used in Example 14, is prepared in a similar manner to that used to prepare the sodium salt of Example 8. From 17 g of (IR, trans) 2,2-dimethyl acid 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylic, 18.27 g of sodium salt are obtained.

The toluene solution of (R) allethrolone methanesulfonate, used in Example 14, is obtained in the same manner as that used in Example 8.

Example 15:

2,2-Dimethyl 3R- (2 ', 2'-difluorovinyl) cyclopropane 1 R-carboxylate of (S) allethrolone or (IR.cis) 2,2-dimethyl 3- (2', 2'-difluorovinyl) cyclopropane 1 (S) allethrolone carboxylate from (R) allethrolone methanesulfonate (without isolation of the intermediate methanesulfonate).

11.5 g of the sodium salt of the acid (1R, cis) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) are introduced into a mixture of 23 cm3 of toluene and 23 cm3 of terbutanol 1-carboxylic cyclopropane,

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626 320 10

added in 1 min 35 cm3 of a toluene solution of allethrolone methanesulfonate titrating 1.13 mol / 1, stirred for 76 h at 20 ° C,

treated analogously to that of Example 8, 12.25 g of crude ester are obtained, which is purified by chromatography on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (9/1 ), and obtains 9.61 g of (1R, cis) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylate from (S) allethrolone; [a] ^ § = + 5 ° (c = 0.8%, chloroform).

Circular dichroism (dioxane) 10

Ae = —18.1 at 226 nm Ae = + 2.6 at 321 nm Ae = + 2.3 at 332 nm

UV spectrum (ethanol)

Max. at 228 nm e = 15,200

The sodium salt, used in Example 15, is prepared in a similar manner to that used to prepare the sodium salt of Example 8. Starting from 10.57 g of acid (1R, cis) 2.2 -dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylic, 11.65 g of sodium salt are obtained.

The toluene solution of (R) allethrolone methanesulfonate, used in Example 15, is identical to that prepared in Example 8.

25

Example 16:

Preparation of an emulsifiable concentrate.

We intimately mix:

- (1 R, trans) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1 (S) allethrolone carboxylate 0.3 g

- piperonyl butoxide 3 g

- topanol A 0.1 g

- xylene 96.6 g

Example 17: 35

Preparation of a smoke spiral.

Carefully incorporate a solution of 0.1 g of (IR, trans) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylate of (S) allethrolone in 5 cm3 of methanol in a mixture consisting of 40 30 g of pyrethrum marc, 12 g of pyrethrum stem powder, 51.1 g of coconut shell powder, 6 g of soluble starch. The powder obtained is kneaded with approximately 100 g of water, dried and shaped into a spiral shape with a thickness of approximately 0.4 cm and a diameter of approximately 12 cm. 45

Example 18:

Preparation of a smoke spiral.

Carefully incorporate a solution of 0.15 g of (1R, cis) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylate of (S) allethrolone in 5 cm3 of methanol in a mixture consisting of 43 g of pyrethrum stem powder, 52 g of coconut shell powder and 4.4 g of soluble starch. The powder obtained is kneaded with approximately 100 g of water, dried and shaped into a spiral shape with a thickness of approximately 0.4 cm and a diameter of approximately 12 cm.

Example 19:

Preparation of a composition intended to be heated

electrically.

A solution of 0.2 g of (1 R, trans) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane (S) allethrolone 1-carboxylate in 5 cm3 of toluene is adsorbed on the surface of '' a piece of rectangular asbestos 2 x 2 x 0.8 cm. A second piece of asbestos of the same size is attached to the piece of asbestos. A smoke composition is thus obtained which will be used by heating it on a plate provided with an electrical resistance.

Study of the insecticidal activity of 2,2-dimethyl 3R- (cyclopentyli-denemethyl) cyclopropane 1 (S) allethrolone R-carboxylate (compound A), of (IR, trans) 2,2-dimethyl 3- (2 ' , 2'-dichlorovinyl) cyclo-propane (S) allethrolone 1-carboxylate (compound B), (IR, trans) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-car-boxylate of (S) allethrolone (compound C), of (1R, cis) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylate of (S) allethrolone (compound D).

A) Study of the knockdown effect on houseflies

The test insects are female house flies 3 days old. The operation is carried out by direct spraying in a Kearns and March chamber, using as solvent a mixture of equal volumes of acetone and kerosene (quantity of solution used: 500 mg).

About 50 insects are used per treatment. The controls are carried out every minute up to 15 minutes.

The result is expressed in KT 50 (knock-time 50), which is the time necessary to kill 50% of the insects with a determined dose of product to be tested. The shorter the time the greater the activity of the product.

The experimental results obtained are summarized in the following table.

Doses in mg / 1 of

Percentage of KD (knock-down)

KT 50

active ingredient

2mn

4mn

6mn

8 mins

10 mins

15mn inmn

Compound A

1000

30.0

83.3

93.3

93.3

96.7

100

2.6

500

13.8

58.5

79.3

79.3

82.8

96.6

3.7

250

0

46.6

83.3

90.0

90.0

90.0

4.3

Compound B

500

32

70

89

100

-

-

2.9

250

12.7

46.5

68.7

84.8

96.9

100

4.3

125

5

14

35

51

68

89

7.5

Compound C *

1000

92

98

100

100

100

100

<1

500

94

98

100

100

100

100

1.16

250

52

96

98

100

100

100

1.7

Compound D *

1000

62

84

100

100

100

100

1.7

500

60

80

100

100

100

100

1.7

250

30

74

100

100

100

100

2.5

Conclusion: Compounds A, B, C, D have good knock-down activity against houseflies. * For compounds C and D, the KT 50 were determined by graphical estimation.

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626320

B) Study of the lethal effect on houseflies

The test insects are houseflies of mixed sexes. One operates by topical application of 1 [il of acetonic solution on the dorsal thorax of insects. 50 individuals are used per treatment. The mortality check is carried out 24 hours after treatment. 5

The compound to be tested is synergized by piperonyl butoxide (10 parts by weight of piperonyl butoxide for 1 part of product to be tested).

Doses in ng of active ingredient per fly

% mortality at 24 h

LD 50 in ng per insect

Compound A

50

90.9

25

72.5

17.5

12.5

28.2

Compound B

250

100

100

86.7

38.0

50

65.6

Compound C

25

100

12.5

53.3

10.1

6.25

16.7

Compound D

175 50 25

100 90 46.6

25.4

Conclusion: The compounds have good lethal activity on houseflies.

C) Study of the insecticidal activity of the Cet D compounds on Aedes aegypti in the form of a fumigant composition

The knock-down effect and the lethal effect of the compound to be tested are studied on females of Aedes aegypti.

We use the Dainippon closed cylinder method. A smoke coil containing the test compound is burnt at one end for 1 min in a closed cylinder 20 cm in diameter and 43 cm high, which contains 20 Aedes aegypti females.

The knock-down effect is observed every 30 s for 5 min. The results are expressed in KT 50 or time required to kill 50 percent of the insects with a determined dose of active ingredient. This time is shorter the greater the activity of the product.

A count is also made of individuals who die after 24 hours and the results of lethal activity are expressed as a percentage of mortality.

3 series of successive tests were carried out and the means of these tests were determined.

The tests are carried out in parallel with a reference product known for its high knockdown activity: the d-trans-chrysanthemate of (S) allethrolone (or compound E).

The experimental results obtained are summarized in the following table:

TEST!

TEST II

TEST III

Average weight

% mortality

KT 50

Doses (1)

KT 50

Mortality

KT 50

Mortality

KT 50

Mortality

medium mean coil

inmn

at 24 hrs in min

at 24 hrs in min

at 24 h burned in mg in 24 h in min

Compound C

0.15

0.60

100

0.75

100

0.75

100

44.5

100

0.70

0.075

1.40

93.8

1.25

100

1.25

100

49.9

97.8

1.30

0.037

1.90

62.5

2.0

80

2.40

52.1

48.5

64.9

2.10

Compound D

0.15

0.75

100

0.75

100

0.75

100

43.0

100

0.75

0.075

1.45

100

1.70

73.6

1.40

100

47.8

91.2

1.55

0.037

1.60

58.8

2.30

75

1.70

78.9

50.6

70.9

1.85

Compound E

0.60

1.40

100

1.15

100

1.65

100

48.2

100

1.40

0.30

2.25

100

2.40

95.7

2.25

100

43.7

98.9

2.30

0.15

2.70

100

3.10

100

2.70

81

47.5

93.4

2.80

Conclusion: The KD activity of compounds C and D is approximately 4 times greater than that of compound E. Compounds C and D also have an interesting lethal activity.

(1) in percentage by weight of active material in the smoke spiral.

R

Claims (2)

626,320 CLAIMS 1. Process for the preparation of esters exerting an insecticidal action, derivatives of cyclopropane / carboxylic acids (A), racemic or optically active, of IR, 3R configurations; IS, 3S; IR, 3S; 1S, 3R, and optically active allethrolone, of configuration (S) or (R), of general formula: (I) (Sour) in which either Ri and R2, which are identical or different, represent alkyl radicals containing from 1 to 3 carbon atoms, or. R, and R2 represent fluorine, chlorine or bromine atoms, ie R, represents an alkyl radical containing 1 or 2 carbon atoms and R2 represents a radical: -Ç-CH, or a radical: -CH, -0-CH, either R and R2 represent together, with the carbon atom to which they are linked, a carbon homocycle comprising from 3 to 6 carbon atoms, or R, and R2 represent together, with the carbon atom to which they are linked, a cycle of formula: in which X represents an oxygen or sulfur atom, characterized in that an optically active allethrolone sulfonate of configuration (in an organic solvent or a mixture of organic solvents) is reacted R) or (S), of general formula: (II) XS 020 '0 (R) or (S) in which X 'represents either an alkyl radical containing from 1 to 3 carbon atoms, or a phenyl radical optionally substituted in the para position by a methyl radical or by a fluorine, chlorine or bromine atom and in which the allethrolone is optically active, of configuration (R) or (S), with a racemic or optically active salt of cyclopropane-carboxylic acid (A), of general formula: q -OH (III) in which R, and R2 retain the abovementioned meanings, in order to obtain the ester of cyclopropanecarboxylic acid (A) and of optically active allethrolone of configuration (S) or (R) antipodal to that of the starting sulfonate. s 2. Method according to claim 1, characterized in that the salt of cyclopropanecarboxylic acid (A) is chosen from the group consisting of alkaline salts, alkaline earth salts, tertiary base salts and the salt of ammonium. 3. Method according to one of claims 1 or 2, characterized in that io the salt of cyclopropanecarboxylic acid (A) is an alkaline salt. 4. Method according to one of claims 1 to 3, characterized in that the salt of cyclopropanecarboxylic acid (A) is chosen from the group consisting of the sodium salt and the potassium salt. 5. Method according to one of claims 1 to 4, characterized in that the organic solvent, or the mixture of organic solvents, is chosen from the group consisting of dimethylformamide, hexamé-thylphosphorotriamide, dimethylsulfoxide, dimethoxyethane , acetonitrile, aliphatic ketones containing from 3 to 6 carbon atoms, alkanols, monocyclic aromatic hydrocarbons, or by a mixture of these solvents. 6. Method according to claim 5, characterized in that the solvent is chosen from the group consisting of hexamethylphospho-rotriamide, dimethylsulfoxide and dimethylformamide. 7. Method according to claim 5, characterized in that the mixture of solvents is a mixture of toluene and dimethyl sulfoxide. 8. Method according to claim 5, characterized in that the mixture of solvents is a mixture of toluene and secondary or tertiary alkanol comprising from 4 to 6 carbon atoms. 9. Method according to claim 8, characterized in that the mixture of solvents is a mixture of toluene and tertiary butanol. 10. Method according to one of claims 1 to 9, characterized in that one uses allethrolone sulfonate in solution without isolating it from the reaction medium in which it was formed. 11. Method according to claim 10, characterized in that the solvent, within which the allethrolone sulfonate is prepared, is a monocyclic aromatic hydrocarbon. 12. Method according to one of claims 1 to 11, characterized in that the cyclopropanecarboxylic acid salt is used in 40 solution, without isolating it from the reaction medium in which it was formed. 13. The method of claim 12, characterized in that the salt of cyclopropanecarboxylic acid is prepared in a solvent, or a mixture of solvents, chosen from the group consisting of 45 dimethylformamide, dimethyl sulfoxide, hexamethylphosphoro-triamide, dimethoxyethane, acetonitrile, aliphatic ketones containing from 3 to 6 carbon atoms, alkanols, monocyclic aromatic hydrocarbons, or by a mixture of these solvents. 14. Method according to one of claims I to 13, characterized in that the cyclopropanecarboxylic acid (A) is chosen from the group consisting of 2,2-dimethyl 3R- (2'-methyl l'- propenyl) cyclo-propane lR-carboxylic acid 2,2-dimethyl 3S- (2'-methyl l'-propenyl) cycIopropane lR-carboxylic acid 2,2-dimethyl 3R- (cyclopentylidenemethyl) cyclopropane lR- carboxylic acid 55 (IR, trans) 2,2-dimethyl 3- {2 '-' 2-dichlorovinyl) cyclopropane 1-carboxylic acid (IR, trans) 2,2-dimethyl 3- (2 ' , 2'-di-fluorovinyl) 1-carboxylic cyclopropane, (1R, eis) 2,2-dimethyl 3- (2'-2'-difluorovinyl) cyclopropane 1-carboxylic acid. 15. Method according to one of claims 1 to 14, characterized in 60 that the starting allethrolone is the configuration allethrolone (R). 16. Method according to one of claims 1 to 14, characterized in that the optically active allethrolone sulfonate starting material consists of a mixture of allethrolone sulfonate of configuration (S) and of allethrolone sulfonate of configuration ( R), rich in "Sulfonate, of configuration (R). 17. Insecticidal composition, characterized in that it contains, as active principle, at least one of the compounds of formula I named below: 3 626320 (S) allethrolone 2,2-dimethyl 3R- (cyclopentylidenemethyl) cyclopropane 1R-carboxylate; 2,2-dimethyl 3S- (2 ', 2'-dichlorovinyl) cyclopropane lR-carboxylate of (S) allethrolone or (IR, trans) (S) allethrolone 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1-carboxylate; 2,2-dimethyl 3S- (2 ', 2'-difluorovinyl) cyclopropane 1R (S) allethrolone carboxylate or (IR, trans) (S) allethrolone 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylate; 2,2-dimethyl 3R- (2 ', 2'-difluorovinyl) cyclopropane 1R-carboxylate of (S) allethrolone or (1R.cis) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylate of (S) allethrolone. 18. Use of the new compounds of formula I named below: (S) allethrolone 2,2-dimethyl 3R- (cyclopentylidenemethyl) cyclopropane 1R-carboxylate; 2,2-dimethyl 3S- (2 ', 2'-dichlorovinyl) cyclopropane lR-carboxylate of (S) allethrolone or (IR, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylated (S) allethrolone; 2,2-dimethyl 3S- (2 ', 2'-difluorovinyl) cyclopropane 1R (S) allethrolone carboxylate or (IR, trans) (S) allethrolone 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylate, and 2,2-dimethyl 3R- (2', 2'-difluorovinyl) cyclopropane 1R-carboxylate S) allethrolone or (lR.cis) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane 1-carboxylate of (S) allethrolone, as insecticidal agents.