DK158655B - PROCEDURE FOR THE PREPARATION OF ESTERS OF (A) -CYCLOPROPANCARBOXYLIC ACIDS, WHICH ARE RACEMIC OR OPTICALLY ACTIVE WITH 1R, 3R, 1S, 3S, 1R, 3S- OR 1S, 3R CONFIGURATION, AND ALSO (R) -configuration - Google Patents

Description

in

DK 158655 B

5 10 15 20

This invention relates to a particular process for preparing esters of cyclopropane carboxylic acids and optically active allethrolone from allethrolone sulfonates of antipodal configuration.

More particularly, the invention relates to a process for the production of esters of the general formula I set forth in claim 1, and this method is peculiar to the characterizing part of claim 1.

This process is called process cC,

The salt of (A) -cyclopropane carboxylic acid used in the process of the invention is preferably selected from a group consisting of the alkali metal salts, the alkaline earth metal salts, the tertiary bases salts and the ammonium salt.

It is particularly advantageous as salt of (A) -cyclopropane carboxylic acid to use an alkali metal salt.

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According to a preferred embodiment of the process of the invention, the salt of (A) -cyclopropane carboxylic acid is the sodium or potassium salt.

Among the acids to which the process according to the invention can be used are especially mention 2,2-diethyl-3- (2, -methyl-1,1-propenyl) -cyclopropane-1-carboxylic acids, 2,2-dimethyl-3- (2 *, 2'-dichlorovinyl) - cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- (2,2-dibromovinyl) oyclopropane-1-carboxylic acids, 2,2-dimethyl-3- (2 *, 2 * -Difluorovinyl) -cyclopropane-1-carboxylic acids, 2,2-dimethyl-3- (2'-methyl-3'-methoxy-10 -1 * (E) -propenyl) -cyclopropane-1-carboxylic acids , 2,2-Dimethyl-3- (21-Ethyl-3 * -oxo-1 * -butyl) -cyclopropane-1-carboxylic acids, 2,2-dimethyl-3- (cyclopentylidenemethyl) -cyclopropane-1-carboxylic acid the carboxylic acids, 2,2-dimethyl-3- (2'-oxo-31-oxacyclopentylidene methyl) -cyclopropane-1-carboxylic acids, 2,2-dimethyl-3- (2 * -oxo-3'-thiacyolopentylidene methyl) - The 15-cyclopropane-1-carboxylic acids, the aforementioned acids being racenic or optically active, and especially the acids used in the examples in the experimental part.

The organic solvent or mixture of organic solvents wherein the condensation of the allethrolone sulfonate 20 and the salt of (A) -cyclopropane carboxylic acid is carried out according to the invention is preferably selected from dimethylformamide, hexamethylphosphorotriamide, dimethylsulfoxide, dimethoxyethane, dimethoxyethane, alkanols, monocyclic aromatic hydrocarbons or a mixture of these solvents.

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

San may advantageously use as a solvent mixture a mixture of toluene and dimethyl sulfoxide.

According to other preferred embodiments of the process according to the invention, the solvent mixture used in the process according to the invention is a mixture of toluene and secondary or tertiary alkanol having 4-6 carbon atoms, especially a mixture of toluene and tert-butanol.

The sulfonates of optically active allethrolone of the general formula II used as the starting product of the process according to the invention are described in French patent application 76-19087 of 23/6 1976.

Pieces of sulfonates are prepared by mixing in an organic solvent or a mixture of organic solvents in the presence of

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of a basic agent, the sulfonic acid chloride of the general formula IV is reacted

X * SO 2 Cl (IV) where Xf has the same meaning as above, i. represents an alkyl group having 1-3 carbon atoms such as methyl, ethyl, propyl or isopropyl, a phenyl group optionally substituted at the β-position with a methyl group or with a fluorine, chlorine or bromine atom, with optically active allethrolone having (R) or (S) configuration.

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

light organic solvent or the mixture of organic solvents used to perform this condensation is preferably selected from aliphatic ketones of 3-6 carbon atoms, monocyclic aromatic hydrocarbons, oxide ethers and 15 chlorinated solvents.

Advantageous working methods consist of using either acetone or toluene as a solvent,

The sulfonic acid chlorides IV used are preferably methanesulfonyl chloride or p-toluenesulfonyl chloride.

Examples of the preparation of sulfonate of optically active all lethrolone are given below in the experimental section.

According to a preferred embodiment of the process according to the invention, the allethrolone sulfonate is used in solution without isolating it from the reaction environment in which it is formed.

Preferably, then, as a solvent is used to prepare the sulfonate of optically active allethrolone a monocyclic aromatic hydrocarbon.

The salt of the cyclopropane carboxylic acid is prepared by conventional methods by the action of acid on the corresponding base in an organic solvent.

According to a preferred embodiment of the invention, the salt of cyclopropane carboxylic acid is used in solution without isolation from the reaction environment in which it is formed.

Preferably, then, in the preparation of the salt of 35 (A) -cyclopropane carboxylic acid, a solvent or mixture of solvents selected from dimethylformamide, dimethylsulfoxide, hexamethylphosphorotriamide, dimethoxyethane, acetonitrile, aliphatic ketones of 3-6 carbon atoms, alkanols, alkanols, alkanes, hydrocarbons or a mixture of these solvents,

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The process according to the invention is used especially in the case where the (A) -cyclopropane carboxylic acid is 2,2-dimethyl-3R- (2t-methyl-1'-propenylJ-cyclopropane-1R-carboxylic acid, 2,2-dimethyl-3S). (2'-methyl-11-propenyl) -cyclopropane-1R-carboxylic acid, 2,2-dimethyl-5 -3R- (cyclopentylidenemethyl) -cyclopropane-1R-carboxylic acid, (IR, trans) - 2,2-dimethyl 3- (2 ', 21-Dichlorovinyl) -cyclopropane-1-carboxylic acid, (1R, trans) -2,2-dimethyl-3- (2', 2 * -difluoro-vinyl) -cyclopropane-1-carboxylic acid and (3R, cis) -2,2-dimethyl-3- (2 ', 2'-difluorvinyi) cyclopropane - 1-carboxylic acid.

It is well known that esters of oyclopropane carboxylic acids and optically active allethrolone with (S) configuration have an insecticidal activity far greater than the action of esters of cyclopropane carboxylic acids and allethrolone which have (R) configuration or are racemic with (R, S) configuration.

To prepare the esters of oyclopropane carboxylic acids and optically active allethrolone with (S) configuration, the only known method has been to esterify a cyclopropane carboxylic acid or one of its functional derivatives with optically active allethrolone with (S) configuration. Optically active allethrolone with (S) configuration has long been unavailable at the industrial level. There are now methods for cleavage of racemic (R, S) -allethrolone enabling allethrolone to be obtained with (S) configuration, see French Patent 2,166,503, with weight yields which, of course, cannot exceed $ 50 relative to the racemic starting salethrolone.

Thus, optically active allethrolone with (R) configuration resulting from this cleavage constitutes a product of no practical utility, and it is of great industrial interest to be able to make use of this allethrolone with (R) configuration again.

The pure process according to the invention presents a particularly advantageous solution to this important industrial problem. In fact, in a single simple reaction step directly from the allethrolone with (R) configuration, it is possible to obtain the esters of the high yield (S) cyclopropane carboxylic acids.

Pure does not offer the advantage over the already known methods of ending up with an isolated allethrolone with (S) configuration, which must then be esterified with the appropriate cyclopropane carboxylic acid (which must be converted into acid chloride in advance). Of course, the process of the invention presents a particular interest when the starting alethrolone is allethroic.

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Ion with (R) configuration *

In addition, the methods of cleavage of allethrolone are not quantitative and in practice, in addition to the desired allethrolone with (S) configuration, yields a mixture of allethrolone with (E) ~ 5 configuration and allethrolone with (S) configuration which is rich in allethrolone with (R) configuration.

After converting these mixtures into sulfonate, a mixture of sulfonate of allethrolone with (R) configuration and sulfonate of allethrolone with (S) configuration rich in allethrc-10 ion with (H) configuration are obtained.

The process of the invention is applied to these mixtures.

The invention thus relates to a process according to the general process a, characterized in that the sulfonate of optically active allethrolone used as a starting product is constituted by a mixture of sulfonate of allethrolone with (S) configuration and sulfonate of allethrolone with (R ) configuration which is rich in sulfonate with (R) configuration.

The method according to the invention has an unexpected character.

Although some examples of inversion of optically active aliphatic alcohols by the action of an acetate on the tosylate of the alcohol were already known, the inversion of the asymmetric center of allethrolone, although of considerable industrial interest, was never realized using this type of method.

Indeed, the success of such an inversion method in the case of allethrolone was highly questionable in the first place, primarily because access to the allethrolone sulfonates presents difficulties. Thus, it is known that the treatment of allethrolone with methanesulfonyl chloride in the presence of a weak base such as pyridine gives the chlorinated derivative and not the sulfonate.

The allethrolone sulfonates, as described in the invention, are fragile products which are sensitive to heat in the presence of inorganic or organic bases which causes them to lose the sulfonyl group and lead to epaling products by Diels - Alder's reaction

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"/ CC

(not insulable) j |

These sulfonates are also sensitive to the presence of hydrochlorides of bases such as the hydrochloride of triethylamine which results in the formation of the ehlorated derivative.

Accordingly, the preparation of the allethrolone sulfonates described in the invention necessitates that the said difficulties be remedied by suitable solutions, i.e., the reaction is carried out at low temperature under limited alkaline conditions and the use of a reaction solvent is used. wherein the triethylamine hydrochloride formed during the sulphonation is insoluble, which makes it unsuitable to react rapidly with the all-throlone sulphonate, Ω

The reaction of the allethrolone sulfonate with a cyclopropane carboxylic acid salt also presents several risks: - Firstly, the development of the sulfonate towards the formation of cleavage products due to the alkalinity imparted by the cyclopropane carboxylic acid salt,

2 S

- partly an incomplete epimerization, which would lead to partial racemization of the asymmetric center of allethrolone.

The process of the invention makes it possible to remarkably reduce the dreaded side reactions and leads with very large yields (both from a chemical and an optical point of view) to the pure products.

By the process of the invention, the following compounds can be prepared: - 2,2-dimethyl-3R- (cyclopentylidenemethyl) -cyclopropane-1S - earboxylic acid (3) -allethrolone ester, 2,2-dimethyl-3S- (21,2f dichlorovinyl) -cyclopropane-1R-carboxylic acid (S) -allethrolone ester or (1R, trans) -2,2-dimethyl-3- (2 *, 2 * -dichlorovinyl) -cyolopropane-1-earboxylic acid (S ) -allethrolone ester, - 2,2-dimethyl-33- (21,2 f-difluorovinyl) -cyclopropane-1R-carboxylic acid (S) -allethrolone ester or (IR, trans) -2,2-dimethyl-3- (2 ', 21-Difluorovinyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester and

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- 2,2-dimethyl-3R- (2 ', 2'-difluorovinyl) -cyclopropane-1R-carboxylic acid (S) -allethrolone ester or (IR, cis) -2,2-dimethyl-3- (2 , 2 * - -Difluorovin ;; 1) -cyelopropane-1-carboxylic acid (3) -allethrolone ester,

Insecticidal activity of the four above-mentioned compounds is shown in a study below.

Thus, these products were found to have a knock-down ability (or ability to knock down the insects), which is extremely valuable. high, while possessing a good lethal effect.

They are particularly applicable in the household. They can also be used in agriculture, especially in this latter case they can be used in conjunction with other pyrethrinoid compounds. Pure insecticidal activity of these products has been demonstrated, for example, by tests with knock-down activity or by tests with lethal effect on houseflies and by experiments with Aedes aegypti. 15 In this last case they have been used, having incorporated those in smoke developing products.

The four above compounds may advantageously be used in conjunction with a synergistic agent such as piperonylbutoxide or N- (ethylheptyl-2-) bicyclo- (2,2,1) -5-hepten-2,3-dicarboxyimide,

The active ingredient (s) may optionally be added to one or more other pesticidal agents. These products may be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible strips, baits or other preparations usually used to recover this kind of compound,

In addition to the active ingredient, these preparations contain \

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usually a carrier and / or a nonionic surfactant which furthermore ensures a uniform distribution of the constituents constituting the mixture. The carrier used may be a liquid such as water, ethanol, hydrocarbons or other organic solvents, a mineral oil or animal or vegetable oil, a powder such as talc, clay, silicates, diatomaceous earth or a solid combustible material such as pyrethrum quas.

These insecticidal compositions preferably contain 0.01-95% by weight of active ingredient.

10 The use of the four above-mentioned compounds in the form of smoke-producing compositions is particularly interesting.

In particular, these products may be constituted by an insecticidal coil containing preferably 0.01 to 10% by weight of at least one of the four above-mentioned compounds as an active ingredient and an inert flammable carrier which is constituted in particular by e.g. pyrethrum kvass, powder of the leaves of Machilus thumbergii, powder of pyrethrum stalk, powder of cedar needles, wood powder, e.g. pine sawdust, starch and powder of coconut shells.

They can also be obtained by incorporating at least one of the four compounds at a concentration of 0.01-95% by weight in an incombustible fibrous substrate, and placing the thus obtained smoke preparation in a heating apparatus, e.g. an electric mosquito extermination composition which aims to evaporate the active ingredient, giving rise to an evaporation which can be extended as desired.

Thus, to obtain such a composition, an atomizable oil containing preferably 0.01-95% by weight of at least one of said compounds can be prepared, this oil being able to soak the wick in a lamp and subject to combustion, which also causes evaporation of the active ingredient, 2,2-dimethyl-3S- (2f, 2'-difluorovinyl) -cyclopropane-1R-carboxylic acid (S) -allethrolone ester or (1 H ) -cyclopropane-1-carboxylic acid (S) -allethrolone ester and 2,2-dimethyl-3D- (2 ', 2'-difluorovinyl) -cyclopropane-1R-carboxylic acid (S) -allethrolone ester or (111,018) -2 , 2- (3111 ^ 1 ^ 1-3- (2 ^ 2 ^ -difluorovinyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester has a particularly interesting activity when used in the form of smoke-generating preparations,

The following examples illustrate the method of the invention.

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Example 1.

2,2-dimethyl 1-3 R- (21-methyl-1 * -propenyl) -cyclopropane-1R-oreboxylic acid-2-allyl-5-methyl-4R-hydroxy-2-cyclopent-1-one or d- trans - ohranthanthemic acid (R) -all throlones ter from methanesulfonate of 5 (S) -allethrolone, Into 33 ml of hexamethylphosphorotriamide 12.5 g of methanesulfonic acid (S) -allethrolone ester are added, 9 * 65 g sodium salt of d-trans-chrysanthemic acid, stirring for 10 minutes, adding a mixture of 1 L sodium hydroxide solution, water and n-heptane, stirring 10, separating the organic phase by decantation, extracting the aqueous phase with heptane, combining the organic phases , wash them, dry them and get 12.94 g of d-trans-chrysanthemic acid (R) -allethrolone ester,

Circular Diohroism (dioxane); Turning Point 345 nm Δε = - 1.18 max 332 nm Δε = - 2.41 max 321 nm Δε = - 2.73 turning point 310 nm Δε = - 2.08 max 230 nm Δε = +15.9 Methanesulfonic acid - ( The S) -allethrolone ester used can be prepared as follows:

Dissolve 7.35 g of (S) -allethrolone in 7.5 ml of acetone, cool to -15 ° C, add 8.4 ml of triethylamine and then slowly 4.3 ml of methanesulfonyl chloride dissolved in 11 ml of acetone, stir for 15 minutes , pour the reaction mixture into a mixture of 23 µl of 1N hydrochloric acid, 56 ml of water and 23 ml of methylene chloride, stir for 15 minutes, separate by decanting the organic phase, extract the aqueous phase with methylene chloride, combine the organic phases, wash them, dry them , evaporates them to dryness to obtain 12.5 g of crude methane sulfonic acid (S) -allethrolone ester, which is used immediately 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- (2β-methyl-1'-propenyl) -cyclopropane-1R -carboxylic acid in 50 ml of acetone introduces the required amount of 10 N aqueous sodium hydroxide solution to obtain the phenolphthalein's cover, isolates by suctioning the precipitate formed, it is washed, dried and obtained 18.6 g of sodium salt of 2.2-d imethy-1 3 R- (2'-methyl-1'-propenyl) -cyclopropane-1R-carboxylic acid, which is used immediately for condensation in Example 1.

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Example 2.

2> 2-Dimethyl 1-3R- (2L-methyl-1 * -propenyl) -cyclopropane-1R-carboxylic acid (S) -allethrolone ester from methanesulfonic acid (R) -allethrolone ester. Working in analogy to Example 1 from methanesulfonic acid (R) -allethrolone ester, 2,2-dimethyl-3R- (2-methyl-1'-propenyl) -cyclopropane-2 1R-Carboxylic Acid (S) - OO r -allethrolone ester, or- -50 ° (o = 5 $, toluene) *

Example 5

2,2-Dimethyl-3R- (2 '-methyl-1' -propenyl) -cyclopropane-1R-carboxylic acid - (R) -allethrolone from methanesulfonic acid (S) -allethrolone

To the solution of potassium salt obtained from 110 g of d-trans-chrysanthemic acid below, a solution of 165 g of methanesulfonic acid (S) -allethrolone in 350 ml of dimethyl sulfoxide is stirred rapidly at 24 ° C. C, add ICO ml of heptane and 500 ml of water, stir, separate by decanting the organic phase, extracting the aqueous phase with heptane, combining the heptane phases, washing them with a 1 E aqueous sodium hydroxide solution and then with water, extracting the aqueous washing liquids with heptane , the heptane fractions are combined, dried, evaporated to dryness by distillation to obtain 169 g of 2,2-dimethyl-3R- (2t-methyl-1,1-propenyl) -eyclo-ΛΛ-propane-1R-carboxylic acid. (R) -allethrolone ester, oT- = + 11 ° (c = 1 $, ethanol).

U.V. spectrum (ethanol) in 25 Max at 225 nm, E ^ = 600, max at 295 nm, = 3.

Circular dichroism (dioxane): - max 230 nm Δε = +15 turning point 310 nm Δε = - 2.15 max 320 nm Δε = - 2.70 30 turning point 330 nm Δε = - 2.43 turning point 345 nm Δε = - 1, 14

Methanesulfonic acid (S) -allethrolone ester used as the starting product in Example 3 can be prepared as follows: 200 g of acetone dissolve 200 g (S) -allethrolone with b.p.

115 ° C / 0.6 mm Hg and - + 14 ° (o = 1.3 $ # chloroform), U.V.absorp

tion (ethanol): max at 229 nm, = 810, add at -15 ° C

114.5 ml of stirred triethylamine introduces between 0 and 5 ° C a solution of 86.5 g of methanesulfonyl chloride in 180 ml of anhydrous acetone over approx. 20 minutes, stirring for 20 minutes at -10 ° C, introducing at -15 ° C 200 ml of methylene chloride and then a mixture of 50 ml

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aqueous 18.8 U hydrochloric acid, stir, separate by decanting the organic phase, extracting the aqueous phase with methylene chloride, combining the organic phases, washing them with water, extracting the aqueous washing liquids with methylene chloride, combining the methylene chloride solutions, washing drying them, evaporating them to dryness under reduced pressure and obtaining 165 g of crude (S) -allethrolone methane sulfonate which is used immediately for the condensation of Example 3 with the potassium salt of d-trans-chrysanthemic acid.

The solution of the potassium salt of d-trans-chrysanthemic acid 10 used in Example 3 can be prepared as follows: Into a mixture of 100 ml of dimethylsulfoxide and 30 ml of water 110 g of 2,2-dimethyl-3R- (2 methyl-1'-propenyl) -cyclopropane - 1R-carboxylic acid, = + 36.7 ° (dimethylformamide), add 2 drops of alcoholic solution of phenolphthalein, add at 15 ° C the required amount of 50 ° B aqueous potassium hydroxide solution to obtain the phenolphthalein pink wrapper (approx. 49.5 ml), add 0.7 ml of water and obtain a solution containing the potassium salt of 2,2-dimethyl-3R- (21-methyl-1'-propenyl) -eyclopropan-R-carboxylic acid.

Example 4.

2'-2-Dimethyl-5R- (2> -methyl-1t-propenyl) -cyclopropane-1R-carboxylic acid - 2-allyl-3-methyl-4S-hydroxy-2-cyclopent-1 -one ester or d-trans - chrysanthemic acid (S) -allethrolone ester from methanesulfonate of (R) -allethrolone.

To a solution of the potassium salt of d-trans-chrysanthemic acid prepared above from 11 g of d-trans-chrysanthemic acid is added at 15 ° C a solution of 16 g of methanesulfonate of (R) -altrolone in 35 ml of dimethyl sulfoxide. stir for 24 hours at 20 ° C, add water and heptane, stir, separate by decanting the organic phase, re-extract the aqueous phase with heptane, combine the organic phases, wash them with 1 E sodium hydroxide solution and then with water, dry evaporating them to dryness to give 16.1 g of 2,2-dimethyl-3R- (2'-methyl-1'-propenyl) -cyclopropane-1R-carboxylic acid (S) -allethrolone ester.

Spectrum (ethanol):

Max 227-228 nm e = 17,400

From this, a $ 94 chemical purity of allethrolone chrysanthemum is deduced.

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Circular dichroism (dioxane):

Max 227.5 nm Δε = -24.5 turning point 310 nm Δε = + 1.87 max 320 nm Δε = + 2.40 max 332 nm Δε = + 2.16 turning point 345 nm Δε = + 1.02

This dichroism corresponds to: 90 # (S) -allethrolone ester 4 # (R) -allethrolone ester plus: 6 $ impurities (according to U.V «spectrum), 10 - which do not affect circular dichroism.

The optical purity of ester egg is thus 90: (90 + 4) = oa.95.8 #. The value for stereo conversion from (R) -allethrolone to (S) -all-lethrolone ester is thus quantitative 95.8: 95.5.

The methane sulfonate of (R) -allethrolone used as the starting product in Example 4 can be prepared as follows:

An (R) -allethrolone with = -15 ° + 1 ° (c = 1 #, chloroform) is used, which according to its circular dichroism contains 95.5 # (R) isomer and 4.5 # (S) isomer .

20 g of (R) -allethrolone are dissolved in 20 ml of acetone, cool to -15 ° C, 11.4 ml of triethylamine is added and then, while maintaining the temperature below 0 ° C, a mixture of 18 ml of acetone and 5.8 ml of methanesulfonyl chloride , stirring for 20 minutes to -10 ° C, introducing methylene chloride, acidifying by adding an aqueous solution 25 of 1 IT hydrochloric acid, stirring, separating the organic phase by decantation, again extracting the aqueous phase with methylene chloride, combining the methylene chloride phases, washing them with water, drying them, evaporating them under reduced pressure to give 16 g of crude (R) -allethrolone methane sulphonate immediately used in Example 4. The solution of potassium salt of d-trans-chrysanthemic acid used in Example 4, can be prepared as follows:

11 g (XR, 3R) -d-trans-chrysanthemic acid is dissolved in 10 ml of dimethyl sulfoxide, 3 ml of water and a drop of alcoholic solution of phenolphthalein are added and potassium hydroxide solution is introduced to cover phenolphthalein.

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Example 5, 2,2-Dimethyl-3R- (2'-methyl-1'-propenyl) -oyolopropane '- 1R-carboxylic acid - (S) -allethrolone ester from methanesulfonate of (R) -allethrolone (without Isolation of the methane sulfonate formed as intermediate).

At 20 ° C, the solution of methanesulfonate of (R) -allethrolone prepared below from 250 g of (R) -allethrolone is rapidly introduced into the solution of the potassium salt of d-trans-chrysanthemic acid prepared below from 293 g of d-trans-chrysanthemic acid, stirring for 24 hours at 20 ° C, adding over 10 minutes at 10 ° C, 20 ° C 750 ml of water, stirring, separating by decanting the organic phase, extracting the aqueous phase with toluene, wash the combined organic phases with water, with an aqueous 1 H sodium hydroxide solution and with water, dry over magnesium sulfate, filter, add 250 g of alumina, stir, filter, evaporate to dryness under reduced pressure to give 400.7 g of 2,2-dimethyl-3R- (2'-methyl-1'-propenyl) -cyclopropane-1R-carboxylic acid (S) -allethrolone ester, α2 ° = -49 ° (c = 5 #, toluene).

The solution of methanesulfonate of (R) -allethrolone used as the starting product in Example 5 is prepared as follows: 250 g of (R) -allethrolone, α2 = -10.5 ° (c = 10 $, chloroform), are dissolved in 750 ml of toluene, introduces 225 g of methanesulfonyl chloride over about 10 minutes at -13 ° C and then, over about 2 hours at -8 ° C, a solution of 217.5 g of triethylamine in 200 ml of toluene, stirring for 15 minutes. minutes, add at -5 ° C over about 30 minutes 25 ml of water, stir, separate by decanting the organic phase, extracting the aqueous phase with toluene, combining the toluene phases, washing them with water, extracting the aqueous washing liquids with toluene, combines the toluene solutions, dries them and obtains a toluene solution of methanesulfonate of (R) -allethrolone, which is immediately used in Example 5.

The solution of potassium salt of d-trans-ohrysanthemic acid used in Example 5 can be prepared as follows: Dissolve 293 g of 2,2-dirnethyl-3R- (2'-trimethyl-1'-propenyl) in 500 ml of dimethyl sulfoxide. -cyclopropane-1R-carboxylic acid, introduces 35 at 40 ° C over about 30 minutes 184.2 g of 50 ° B aqueous potassium hydroxide solution, stirs for 30 minutes at 40 ° C and obtains a solution of the potassium salt of 2.2 diraethyl-3R- (2'-methyl-1'-propenyl) - cyclopropane-R-carboxylic acid.

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Example 6

2,2-Dimethyl-3R- (2 '-methyl-1 * -propenyl) -cyolopropane-1R-carboxylic acid - (R) -allethrolone ester from the methanesulfonate of (S) -allethrolone (without isolation of the intermediate methanesulfonate) ).

From 250 g of (S) -allethrolone, α2 ° = + 14 ° (c = 1.3 / «, chloroform), a toluene solution of methanesulfonate of (£) - allethrolone is prepared, working in analogy with Example 5 and after condensation with the potassium salt of d-trans-chrysanthemic acid, used in solution, following a procedure analogous to Examples 5, 10, 397 g of 2,2-dimethyl-3R- (2'-methyl-1'-propenyl) are obtained. -oyclopropane-1R - carboxylic acid (R) -allethrolone ester, α ^ = -4 ° (c = 5 /, toluene).

Example 7 2,2-Dimethyl-5R- (2 * -methyl-1T-propenyl) -ocyclopropane-1R-carboxylic acid-15 (S) -allethrolone ester from the methanesulfonate of (R) -allethrolone (without isolating it as intermediate formed methanesulfonate).

In the solution of potassium d-trans-chrysanthemate obtained from 82.8 g of d-trans-chrysanthemic acid prepared below, at 18-20 ° C, for a few minutes, the below from 50 g (R) -all-20 is introduced. throlone prepared solution of methanesulfonate of (E) -allethroline, stirring vigorously for 35 hours at 18-20aC, adding 150 ml of water, separating by decanting the toluene phase, extracting the aqueous phase with toluene, combining the toluene phases, washing them with water, combining the toluene phases, wash them until the absence of chrysanthemic acid, using an aqueous solution containing 5 / sodium bicarbonate and 5 / sodium carbonate, and then with water until neutrality, dry, filter, add C, 1 g of hydroquinone to the filtrate, evaporate to dryness by distillation under reduced pressure to obtain 92.9 g of 2,2-dimethyl-3R- (2'-methyl-1'-propenyl) -cyclopropane-1R-carboxylic acid 30 - (S) -allethane brolone ester, α2β = -50.5 ° (c = 5 /, toluene).

The solution of methanesulfonate of (R) -allethrolone used in Example 7 is prepared as follows: X 150 ml of toluene is introduced with 50 g of (?) -Allethrolone and then within a period of 10 minutes at 0 ° C 45 g of methanesulfonyl chloride, 35 g. then adds over the course of approx. For 1 hour at C, a solution of 43.5 g of triethylamine in 40 ml of toluene, stirring for 30 minutes at 0 ° C, introducing at 0 ° C over approx. 30 minutes 200 ml of water, stir, separate by decanting the toluene phase, washing it with water until absent of chloride, working at a temperature below 5 ° C, drying the toluene solution, filtering and obtaining a solution of methanesulfonic acid.

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per night of (R) -allethrolone used immediately in Example 7- for condensation with the potassium salt of cbrysanthemic acid.

The solution of the potassium salt of d-trans-chrysanthemic acid used in Example 7 can be prepared as follows: In a mixture of 100 ml of tert, butanol and 100 ml of toluene, 24.9 g of 90.8 g are added at 20 ° C. s potassium hydroxide solution, adds about 82.8 g of 2,2-dimethyl-3R- (2'-methyl-1'-propenyl) -cyclopropane-1R-carboxylic acid in about # 30 minutes at 25-30 ° C, stirring in 2 hours 30 minutes at 25-30 ° C, cool to 20 ° C and obtain a solution of the potassium salt of 2,2-dimethyl-3R- (2'-methyl-1'-propenyl) -cyclopropane-1R -carboxylic acid, which is used immediately in Example 7 «

Example 8 »2,2-Dimethyl-3S- (21-methyl-1, -propenyl) -cyolopropane-1R-carboxylic acid-15 - (S) -allethrolone ester from the methanesulfonate of (R) -allethrolone (without isolating it as intermediate formed methanesulfonate).

To a mixture of 20 ml of toluene and 20 ml of tert-butanol is introduced 10 g of sodium salt of 2,2-dimethyl-3S- (2 L-methyl-1,1-propenyl) cyclopropane-1R-carboxylic acid and then fast 31.8 ml tcluenop solution of 1.1 moles per ml. liters of methanesulfonate of (R) -allet brolone, stir for 2 hours, add 30 ml of toluene and 20 ml of tert-butanol, stir for 65 hours, add water, extract with ether, wash the ether extracts with water, with a dilute aqueous ammonia solution and with water, dries, evaporates to dryness by distillation under reduced pressure to give 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 7.38 g of 2,2-dimethyl-3S- (2,1-methyl-1'-propenyl) -cyclopropane-1R-carboxylic acid (S) -allethrolone ester, α2 · + - 39.5 ° (c = 0 , 8fo, chloroform.), 30 Circular dichroism (dioxane): Δε = -9.85 at 231 nm Δε s + 2.68 at 320 nm Δε = +2.38 at 332 nm

The sodium salt of cis-chrysanthemic acid used in Example 8 is prepared as follows: 20 g of 2,2-dimethyl-5S- (2f-methyl-1'-propenyl) -cyclopropane-1R are introduced into 200 ml of ethanol. -carboxylic acid and some phenolphtfca clay crystals, slowly add concentrated sodium hydroxide solution until wrapped to pink, eliminate the solvents by distillation under reduced pressure and obtain 22 g of sodium salt of

16 DK 158655B

2,2-aimethyl-3S- (2'-methyl-l'-propenylJ-oyclopropan-le-oarboxylsyre,

The toluene solution of methanesulfona, t of (R) -allethrolone used in Example 8 is prepared as follows: In 105 ml of toluene 35 g of freshly rectified (R) -5-allethrolone (b.p. 97 ° 0 / 0.2) is introduced. , stirring, cooling to 2 ° C, adding 22 ml of methanesulfonyl chloride over 15 minutes at 2 ° C, introducing a mixture of 28 ml of toluene and 42 ml of triethylamine over a period of 1 hour at 2 ° C, stirring for 30 minutes. minutes at 0 ° C, over 10 minutes at 0 ° C, add 35 ml of ice-cold water, then at one time 10 100 ml of ice-cold water, stir, separate by decanting the usual phase from the organic, washing the organic phase with water at 0 ° G, drying the toluene phase, filtering and storing the obtained solution at 0 ° C. Thermal solution contains 1.13 moles of methanesulfonate of allethrolone per liter.

15

Example 9 «2 C2-Dimethyl-5S- (2 * -methyl-11-propenyl) -cyolopropane-1R-oreboxylic acid (S) -allethrolone ester from p-toluenesulfonate of (R) -allethrolone .

To a mixture of 20 ml of dimethyl sulfoxide and 2 ml of vana is introduced 2.28 g of sodium salt of 2,2-dimethylcyl-3S- (2f-methyl-1,1-propanol) cyclopropane-1R-carboxylic acid and then 3.4 g of p-toluenesulfonate of (R) -allethrolone, stir for 2 hours at room temperature, pour in hydrochloric acid, stir, extract the aqueous phase with petroleum ether (bp 35-75 ° C), wash the organic extracts with water, dry, evaporate to dryness to obtain 3.4 g of residue which is chromatographed on silica gel eluting with a mixture of benzene and ethyl acetate (9: 1) to give 2.06 g of 2, 2-dimethyl-3S- (2'-methyl-t-propenyl) - cyclopropane-LR-carboxylic acid (S) -allethrolonester.

Circular dichroism (dioxane); 30 Δε = -7.8 at 233 nm Λ, ε = +2.4 at 320 nm Δε = + 2.1 at 332 nm

The sodium salt of cis-chrysanthemic acid used in Example 9 is prepared in the same manner as in Example 8.

The p-toluenesulfonate of (R) -altreclone used in Example 9 is prepared as follows: Into 100 ml of tetrahydrofuran containing 11.6 g (R) -allethrolone is introduced at -50 ° C under inert atmosphere 11, 6 g of triethylamine and then 21.9 g of p-toluenesulfonyl chloride, stir for 48 hours at 5 ° C, pour the reaction mixture into 0.1 L of hydrochloric acid, stir

IV DK 158655B

about, extracting the aqueous phase with chloroform, washing the organic extracts with water, drying, evaporating to dryness, ehromatographing the residue (29 g) on silica gel eluting with a mixture of benzene and ethyl acetate (955 5) to obtain 6.8 g p-toluenesulfonate of (R) -allethro-5 ion.

Example 10.

2,2-Dimethyl-3S- (2'-methyl-1'-propenyl) oyolopropane-1R-carboxylacetic acid (S) -allethrolone ester from p-bromobenzene sulfonate of (R) -allethrolone To a mixture of 38 ml of dimethyl sulfoxide and 3.8 ml of water is introduced 3.8 g of sodium salt of 2,2-dimethyl-3S- (2'-methyl-1,1-propanyl) -cyclopropane-1R- carboxylic acid, introduces 3.77 g of p-bromobenzene sulfonate of (R) -allethrolone and 5 ml of dimethylsulfoxide, stirs for 30 minutes, leaves for 15 minutes, adds 1 E hydrochloric acid, extracts the aqueous phase with petroleum ether (b.p. 35-75 ° C), wash the organic phases with 1 E sodium hydroxide solution and with water, dry, evaporate to dryness and obtain 1.02 g of residue which is chromatographed on silica gel eluting with a mixture of petroleum ether (bp 35-75 ° C) and ethyl ether (7: 3) to give 0.422 g of 2,2-dimethyl-38- (21-methyl-1'-propenyl) -cyclopropane-1R-carboxylic acid (3 ) - -allethrolone ester.

Circular Diohroism (dioxane): Δε = -3.4 at 233 nm Δε s + 1.5 at 321 nm 25 Δε = +1.7 at 332 nm

The sodium salt of cis-ehrysanthemic acid used in Example 10 is prepared in the same manner as in Example 8,

P-bromobenzene sulfonate of (R) - allethrolone used in Example 10 is prepared as follows: In 25 ml of tetrahydrofuran 2.5 g of (R) -allethrolone are cooled, cooled to 0 ° C, 2.5 g of triethylamine is added and then 6.3 g of p-bromobenzene sulfonyl chloride, stirring for 6 hours at 5 ° C, is added rapidly. hydrochloric acid, stir, extract with methylene chloride, wash the combined organic phases with water, dry, evaporate to dryness and give 7.47 g of crude p-bromobenzene sulfonate of (R) -allethrolone, which is used immediately in Example 10,

is DK 158655B

Example 11, 2,2-Dimethyl-3R- (oyolopentylidene methyl) -cyolopropane-1R-carboxylic acid 2-allyl-3-methyl-4S-hydroxy-2-oyclopent -l-ester ((S) -allethro-lone ester) from the methanesulfonate of (R) -allethrolone.

The 0.530 g of methanesulfonate of (R) -allethrolone prepared below is dissolved from 0.362 g of (R) -allethrolone in 10 ml of dimethylformamide, cooled to 5 ° 0, the 0.576 g of potassium salt obtained below is added, 2-dimethyl-3R- (cyclopentylidene methyl) -1R - carboxylic acid, stirring at 5 ° C for 1 hour, pouring into water, acidifying to 10 a pH of 4 by adding dilute hydrochloric acid, extracting with petroleum ether, drying the organic phase and evaporator, chromatograph the residue on silica gel eluting with a mixture of benzene and ethyl acetate (95 s5) and isolating 0.443 g of 2,2-dimethyl-3R - (cy clopentylidene methyl) -cycelopropane-1R-carboxylic acid (S) -allethrolone ester with = -38 ° + 2.5 ° (c = 0.6 $, chloroform).

Circular dichroism (dioxane): turning point at 345 nm Δε = + 1.09 max at 332 nm Δε = + 2.32 max at 320 nm Δε = + 2, -60 20 turning point at 310 nm Δε = + 1.97 max at 230 nm Δε = -26.7

The methanesulfonate of (R) -allethrolone used as the starting product in Example 11 can be prepared as follows:

Dissolve 0.362 g (R) -allethrolone (which, after its circular dichroism, has an optical purity of 97-98 °) in 4 ml mixture of benzene and ether (50:50), cool to -6 ° C, add 0.46 ml of triethylamine and then slowly 0.2 ml of methanesulfonyl chloride dissolved in 2.7 ml of mixture of benzene and ether (50:50), stirring for 2 hours at -10 ° C, pouring in dilute hydrochloric acid, separating the organic phase By decantation, the aqueous phase is extracted with ether, combines the organic phases, washed with water, dried, evaporated to dryness under reduced pressure and obtained 0.530 g of methane sulfonate of (R) -allethrolone in the crude state, which immediately is used in Example 11.

The potassium salt of 2,2-dimethyl-3R- (cyclopentylidene methyl) -cyclopropane-1R-carboxylic acid used in Example 11 is prepared as follows:

Lian produces 0.576 g of 2,2-dimethyl-3R- (cyclopentylidene methyl) -cyclopropane-1R-carboxylic acid potassium salt by neutralizing a methanolic solution of 2,2-dimethyl-3R- (eyclopentylidene)

19 DK 158655B

methyl) -cyclopropane-1R-oreboxylic acid with methanolic potassium hydroxide solution (phenolphthalein wrap), distillation to dryness under reduced pressure and over distillation by benzene, Example 12.

2,2-dimethyl, yl-3S- (2,2,2-dichlorovinyl) -cyolopropane-1R-carboxylic acid - (S) -allethrolone ester or (1R <trans) -2,2-dimethyl-5- (2 2,2-D-Chloro-Vibyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester from methanesulfonate of (R) -allethrolone (without isolation of the methanesulfonate formed as an intermediate), in a mixture of 20 10 ml of sodium salt of (IR, trans) -2,2-dimethyl-3- (21,2'-dichlorovinyl) -cyclopropane-1-carboxylic acid and then 26.2 ml of toluene and 20 ml of tert-butanol are introduced. ml of toluene solution of methanesulfonate of (R) -allethrolone at a strength of 1.3 moles per liter, stirring 2 hours, adding 30 ml of toluene and 20 ml of tert -butanol, stirring for 65 hours, treating by analogy with Example 8 gives 9.26 g of crude ester which is chromatographed on silica gel eluting with a mixture of cyclohexane and ethyl acetate (9: 1) to give 7.91 g (IR, trans) -2,2-dimethyl-3- (2 *, 2'-dichlorovinyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester, α a = -26 (c = 0.5 $, chloroform),

Circular Diohroism (dioxane): Δε = -23.6 at 228 nm Δε = +2.62 at 321 nm 25 Δε = +2.32 at 332 nm

The sodium salt of (1R, trans) -2,2 ~ -dimethyl-3- (2,1,2'-dichlorovinyl) -cyclopropane-1-carboxylic acid used in Example 12 is obtained as follows: 20 g of ethanol are introduced into 20 g. (IR, trans) -2,2-Dimethyl-30-3 - (2% 2t-dichlorovinyl) -cyclopropane-1-carboxylic acid, some phenol-phthalein crystals, slowly add sodium hydroxide until pink, evaporates to dryness by distillation under reduced pressure, add benzene, evaporate to dryness, perform this operation once more and obtain 22.6 g of sodium salt of (IR, trans) -2,2-35-dimethyl-3- (2 *, 2'-dichlorovinyl] cyclopropane -l-carboxylic acid.

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

so DK 158655B

Example 13 "2.2-Dimethyl-3S- (2f, 2" -dichlorovinyl) cyolopropane-1R-carboxylic acid - (S) -allethrolone ester or (1R "trans) -242-dimethylphayl-5 ~ (2>, 2t") -chlorvinyl) -cyclopropane-1-arboxyl3-acid (S) -allethrolone ester from 5 p-toluenesulfonate of (R) -allethrolone.

To a mixture of 20 ml of dimethyl sulfoxide and 2 ml of water is added 2.78 g of sodium salt of (1R, trans) -2,2-dimethyl-5- (2,2,2-di-chlorovinyl) -cyclopropane-1-one. carboxylic acid and then 3.4 g of p-toluene sulfonate of (R) -allethrolone, stir for 2 hours at room temperature, 10 acids, extract with petroleum ether (bp 35-75 ° C), wash the organic phases with 1 R sodium hydroxide and then with water, dry them, evaporate them to dryness and give 3 g of residue which is chromatographed on silica gel eluting with a mixture of benzene and ethyl acetate (9: 1) to give 2.31 g (1R, trans) -2,2-dimethyl-3- (2 ', 2 * -dichlorovinyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester.

The rat sodium salt of (IR, trans) -2,2-dimethyl-3- (2:, 21-dichlorovinyl) -cyclopropane-1-carboxylic acid is obtained in the same manner as in Example 12.

P-toluenesulfonic acid (R) -allethrolone ester used in Example 13 is obtained as in Example 9.

Example 14.

2,2-Dimethyl-3S- (21,2t-difluorovinyl) -oyolopropane-1R-carboxylic acid - (S) -allethrolone ester or (1R.trans) -2,2-dimethyl-3- (2 *, 2 * -difluorobenzine) .vl) -cyolopropane-1-oreboxylic acid (S) -allethrolone ester from the methanesulfonate of (R) -allethrolone (without isolation of the intermediate methanesulfonate).

In a mixture of 36 ml of toluene and 36 ml of tert-butanol 18.26 g of sodium salt of (1R, trans) -2,2-dimethyl-3- (21,2'-difluorovinyl) cyclopropane are added. 1-carboxylic acid and in 1 minute add 54.5 ml of toluene solution of methanesulfonate of (R) -allethrolone at a strength of 1.13 moles per ml. liters, stirred for 76 hours at 20 ° C, treated in the same manner as in Example 8 to obtain 18.69 g of crude ester which is chromatographed on silica gel eluting with a mixture of cyclohexane and ethyl acetate (9: 1), and 15.1 g (1R, trans) -2,2 - dimethyl-3- (2 *, 2 * -difluorovinyl) -cyclopropane-1-carboxylic acid (3) -allethrolone ester, α 5 ° (c = 1 $, chloroform).

Circular dichroism (dioxane): Δε = -22.6 at 225 nm Δε = + 2.51 at 320 nm Δε = + 2.23 at 332 nm

21 DK 158655 B

U, V, spectrum (ethanol); max at 228 nm ε = 15,300

The sodium salt used in Example 14 is prepared by analogy with the preparation of the sodium salt of Example 8. From 17 g of 5 (IR, trans) -2,2-dimethyl-3- (2 *, 2, -difluorovinyl) -cyclopropane-1- carboxylic acid gives 18.27 g of sodium salt.

The toluene solution of methanesulfonate of (R) -allethrolone used in Example 14 is obtained in the same manner as in Example 8, Example 15.

2'-2-Dimethyl-5R- (21.2, ~ difluorovinyl) - cyolopropane-1R-oreboxylic acid - (S) -alethololone ester or (1R <cis) -2 <2-dimethyl-5- (2t.2t difluoro-vinyl) -cyclopropane-1-oreboxylic acid (S) -allethrolone ester from the methanesulfonate of (E) -allethrolone (without isolation of the methanesulfonate formed as an intermediate).

To a mixture of 23 ml of toluene and 23 ml of tert-butanol is added 11.5 g of sodium salt of (1R, cis) -2,2-dimethyl-3- (2 ', 2'-difluoro-vinyl) cyclopropane. 1-carboxylic acid, in 1 minute add 35 ml of toluene solution of methanesulfonate of allethrolone at a strength of 1.13 moles per liter, stir for 76 hours at 20 ° C, treat in analogy with Example 8 and obtain 12 25 g of crude ester which is purified by chromatography on silio gel eluting with a mixture of cyclohexane and ethyl acetate (9: 1) to give 9.61 g (1R, cis) -2,2-dimethyl 3- (2 ', 2'-Difluorovinyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester α 2 + + 5 ° (c = 0.8 +, chloroform).

Circular dichroism (dioxane): Δε = -18.1 at 226 nm Δε = + 2.6 at 321 nm Δε = + 2:, 3 at 332 nm 30 U, V, spectrum (ethanol): max at 228 nm ε = 15200

The sodium salt used in Example 15 is prepared by analogy with the sodium salt of Example 8. From 10.57 g (1R, cis) -2,2 - dimethyl-3- (2f, 2'-difluorovinyl) cyclopropane-1-carboxylic acid is obtained. 11.65 g of sodium salt.

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

22 DK 158655 B

Example 16.

Preparation of an emulsifiable concentrate.

Thoroughly mix: - 1E., Trans-2,2-dimethyl-3- (2 ', 2f-difluorovinyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester G, 3 g - piperonylbutoxide 3 g - Topanol A 0.1 g - xylene 96.6 g Example 17

Manufacture, of a smoke coil.

Carefully incorporate a solution of 0.1 g of 1R, trans - 2,2-dimethyl-3- (2 *, 2'-difluorovinyl) cyclopropane-1-carboxylic acid (S) -allethrolone ester in 5 ml of methanol in a mixture of 15 30 g of pyrethrum quasi, 12 g of pyrethrum powder, 51 »! g of coconut shell powder and 6 g of soluble starch «The obtained powder is mixed with about 100 g of water, dried and shaped into a spiral with a thickness of about 0.4 cm and 1 diameter of about 12 cm.

Example 18.

Removal of a smoke coil.

Carefully incorporate a solution of 0.15 g of 1R, cis-2,2-dimethyl-3- (2,2,2-difluorovinyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester in 5 ml of methanol in a mixture of 43 g of pyro-thrumstick powder, 52 g of coconut peel powder and 4.4 g of soluble starch. 100 g of water, dry it and form it into a spiral with a thickness of approx. 0.4 cm and a diameter of approx. 12 cm.

Example 19.

Manufacture of a product for electric heating.

A solution of 0.2 g of 1R, trans-2,2-dimethyl-3- (2 *, 2 * -difluorovinyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester is adsorbed in 5 ml of toluene. the surface of a piece of asbestos with the dimensions 2 x 2 x 0.8 cm. Another piece of asbestos with the same dimensions is placed on the piece of asbestos. He thus obtains an evaporative composition which is to be used for heating on a plate with an electrical resistance.

23 DK 158655 B

Investigation of the insecticidal effect of 2,2-dimethyl-5R- (oyclopentylidenemethyl) -oyolopropane-1R-carboxylic acid (S) -allethrolone ester (compound A), of 1R.trans-2 <12-dimeth. yl-3-j (2tt2t - dichlorovin, yl) - cyclopropane-1-carboxylic acid (S) -allethrolone ester (compound B). , of 5 IR, trans -2,2-d-dimethyl-5- (2,221 µl of fluorovinyl) -cyclopropane-1-carboxylic acid (S) -allethrolone ester (forb, O) and of 1R 1, cis-2,2-dimethyl --- 3- (2 ', 2' -difluorovinyl) -cyclopropane-1-oreboxylic acid (S) -allethrolone ester (compound D).

A) Investigation of the knock-down effect on housefly, 10 The test insects are 3 day old female flies. They work by direct atomization in Kearns and March's chamber, using as a solvent a mixture of equal volumes of acetone and petroleum (amount of solution used: 500 mg).

About 50 insects are used per treatment. 15 checks are performed every minute until 15 minutes.

The result is expressed in KT 50, which is the time needed to knock down $ 50 of the insects with a specific dose of the product being tested. This time is shorter the more active the product is, 20 The experimental results obtained are shown in the following table: 25 30 35

24 DK 158655 B

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25, DK 158655 B

B) Investigation of lethal effect on housefly.

The experimental insects are mixed-sex living flies. Topical application of 1 μΐ acetone solution to the insect's dorsal thorax is performed. 50 individuals are used per day. treatment. Mortality is checked at 24 hours after treatment.

Bone compound to be tested is synergetized by piperonyl butoxide (10 parts by weight of piperonyl butoxide for each part by weight of the product to be tested).

10

Bosses in mortality Bl 50 in ng active after 24 hours per day. insect material per fly _ _ 15

Compound A 50 90.9 25 72.5 17.5 12.5 28.2

Compound B 250 100 20 100 86.7 38.0 50 65.6

Compound C 25 100 12.5 53.3 10.1 25 6.25 16.7

Compound B 175 100 50 90 25.4 25 46.6 30 Conclusion: The compounds have a good lethal effect on housefly.

26 DK 158655B

G) Investigation of insecticidal effect of the compounds P..g.gJ ?.

• on Aedes aegypti in the form of smoke preparation.

The knock-down effect and the lethal effect of the compound to be examined are investigated on females of Aedes 5 aegypti.

The closed-cylinder method according to Dainippon is used and a smoke coil containing the compound in question is fired from the end for 1 minute in a closed cylinder of 20 cm diameter and 43 cm height and containing 20 females of Aedes aegypti.

The knock-down effect is observed every 30 seconds for 5 minutes. The results are expressed in K3? 50, that is, the required time to knock down $ 50 of the insects with a specific dose of active substance. This time is shorter the more active the product.

The dead individuals are also counted after 15 24 hours and the lethal effect results are expressed in $ mortality.

Three consecutive rows of tests are performed and the averages of these tests are determined.

The experiments are carried out in parallel with a reference product 20 known for its high knock-down effect, namely d-trans-chry-santhemic acid (S) -allethrolone ester (compound E).

The experimental results obtained are shown in the following table.

25 30 35

27 DK 158655 B

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Claims (15)

28 DK 158655B Patent claims. 1, Process for the preparation of esters of (A) -cyclopropane arboxylic acids which are racemic or optically active with 1R, 3R, 5S, 3S, 1R, 3S or 1S, 3R configuration, and optically active allethro lon with (S) or (R) configuration and of general formula I Process according to claim 1, characterized in that the salt of (A) -cyclopropane carboxylic acid is selected from alkali metal salts, alkaline earth metal salts, tertiary base salts and the ammonium salt. Process according to claims 1-2, characterized in that the salt of (A) -eyclopropane arboxylic acid is an alkali metal salt. Process according to claims 1-3, characterized in that the salt of (A) -cyclopropane carboxylic acid is selected from the sodium and potassium salt * 35 Process according to claims 1-4, characterized in that the organic solvent or the mixture of organic solvents is selected from dimethylformamide, hexamethylphosphoric triamide, dimethylsulfoxide, dimethoxyethane, acetonitrile, alipbatic ketones of 3-6 carbon atoms, alkanols and monocyclic aromatic hydrocarbons. mixture of these solvents. 30,., DK 158655B Process according to claim 5, characterized in that the solvent is selected from hexamethylphosphoric triamide, dimethylsulfoxide and dimethylformamide. Process according to claim 5, characterized in that the mixture of solvents is a mixture of toluene and dimethyl sulfoxide. Process according to claim 5, characterized in that the mixture of solvents is a mixture of toluene and secondary or tertiary alkanol having 4-6 carbon atoms, Method according to claim 8, characterized in that the mixture of solvents is a mixture of toluene and tert-butanol, Process according to claims 1-9, characterized in that allethrolone sulfonate is used in solution without isolating it from the reaction environment in which it is formed. 10. Vs. G (S) or (R) (I) 15 1 2 wherein either R and R «being the same or different represent alkyl- 1 w groups having 1-3 carbon atoms, or R and R represent fluorine, chloro- or bromine atoms, or R "*" represents an alkyl group of 1-2 carbon atoms and R represents the group Or R and R represent together with the carbon atom to which they are 12 bonded, a homocyclic ring of 3-6 carbon atoms, or R and R represent together down the carbon atom to which they are attached, a ring of the formula 30 i ^ Y ° where X represents an oxygen or sulfur atom, k denoted by converting an optically active in an organic solvent or a mixture of organic solvents allethrolone sulfonate of (R) or (S) configuration and of the general formula II 29 DK 158655 B H3C \ "[(II) I (R) or 3? (S) cyclohexo where X * denotes either an alkyl group having 1-3 carbon atoms or a phenyl group optionally substituted at the β-position by a methyl group or with a fluorine, chlorine or bromine atom, and wherein the allethrolone is optically active with (R) or (S) configuration, with a racemic or optically active salt of (A) -oyclopropane carboxylic acid of formula III O 15 Η, α. Λ-OH;> kzn y (III) 20 1 2 wherein R and R have the same meaning as above, to obtain the ester of (A) -cyolopropane carboxylic acid and optically active allethrolone down (S) or (R) configuration and antipodal relative to starting sulphonate sts. Process according to claim 10, characterized in that the solvent in which the allethrolone sulfonate is prepared is a monocyclic aromatic hydrocarbon, Process according to claims 1-11, characterized in that the salt of cyclopropane carboxylic acid is used without isolation from the reaction environment in which it is formed. Process according to claims 1-12, characterized in that the (A) -cyclopropane carboxylic acid is selected from a group consisting of 2,2-dimethyl-3R- (2 * -methyl-1'-propenyl) -cyclopropane-1R-carboxylic acid. 2,2-dimethyl-3S- (2'-methyl-1'-propenyl) -cyclopropane-1R-carboxylic acid, 2,2-dimethyl-3R- (cyclopentylidenemethyl) -cyclopropane-1R carboxylic acid, (IR, trans) -2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) -cyclopropane-1-carboxylic acid, (IR, trans) -2,2-dimethyl-3- (2) ', 2' - (Difluorovinyl) -cyclopropane-1-carboxylic acid and (IR, cis) -2,2-dimethyl-3- (2 ', 2-D-fluoro-vinyl) -ocyclopropane-1-carboxylic acid. Process according to claims 1-13 »characterized in that the starting allethrolone is allethrolone with (R) configuration, Process according to claims 1-13, characterized in that the optically active starting allethrolone sulfonate is constituted by a mixture of sulfonate of allethrolone with (S) configuration and sulfonate of allethrolone with (R) configuration and rich in sulfonate with ( R) configuration.