HRP970570A2 - Arthropodicides and process for their preparation - Google Patents

Description

This invention relates to an arthropodicidal actoparasiticidal composition containing one or more representatives of the 1S-trans, (1S-trans)αS or (1S-trans)α(R,S) isomers or a racemic isomeric mixture (1S-trans)αS(lR- trans)αR of one or more compounds of the cyclopropane-carboxylic acid ester type, which contain two asymmetric centers in the cyclopropane ring and optionally one or more further asymmetric centers in other parts of the molecule, in the amount of 0.001-99 wt. %, optionally mixed with up to 100 wt. % of one or more auxiliaries, primarily antioxidants, stabilizing reagents, wetting agents, emulsifying agents, dispersing agents, anti-foaming agents, diluents and/or fillers, their preparations and the preparation process of said isomers.

Compounds of the above structure include all molecules whose chemical structure was already known prior to the filing date of our application.

Living organisms taxonomically classified as Arthropoda (Articulata) form a huge genus whose members are pests and parasites in humans and domestic animals, or vectors of human and animal diseases, and therefore have great importance in veterinary medicine and public health due to their direct harmfulness or due to the transmission of pathogens that they cause animal and human diseases, associated with serious economic and epidemiological problems. The most harmful among them are the order of animal lice (Phthiraptera), the order of holometabolic insects characterized by one pair of membranous wings (Diptera), the order of fleas (Siphonaptera) and the order of mites (Acarina). The following species are particularly harmful: 1. Damlinia (Bovicola) bovis, Felicola . , Musca domestica, M. autumnalis, Hydotaea irritans, Stomoxys calcitrans, Haematobia irritans, Haematobia exigua, Glossina spp., Lucilia spp., Phormia spp., Callophora spp., Sarcophaga, Hypoderma spp., Gasterophilus spp., Dermatobia, Hippobosca spp. ., Melophagus ovinus (Diptera), 3. Pulex irritans, Sphylopsyllus cuniculi, Xenopsylla spp., (Siphonaptera), 4. Ixodes ricinus, I. holocyclus, I. rubicundus, I. scapularis, Haemophysalis longicornis, Haemophysalis punctata, Dermacentor reticulaatus, Amyloma spp., Boophylus microplus, Hyalomma spp., Ripicephalus appendiculatus, Ripicephalus sanguineus, Argas peersicus, Sarcoptes spp., Demodex spp., Psoroptes spp. (Acarina).

In addition to protective sanitary measures, preparations containing organic compounds with a pesticidal effect can be used to kill or control the above-mentioned Arthropods. Such preparations are chlorinated hydrocarbons (e.g. DDT, methoxychlor), esters of organic phosphoric acids (e.g. bromophos, diazinon, fenthion), carbamate pesticides (e.g. dioxycarb, methomyl, propoxur), pyrethroids (e.g. cypermethrin, deltamethrin fenvalerate, permethrin), amidine-type compounds (e.g. chlordimeform, amitraz) or carbamide derivatives that interfere with cuticle formation (e.g. diflubenzur).

Preparations used to kill or control the above-mentioned Arthropods in the human and animal environment must meet the following criteria:

- effective dose as low as possible;

- biological availability aligned with the life cycle of the above-mentioned ectoparasites;

- absence of accumulation in humans and domestic animals;

- minimal toxicity for warm-blooded creatures;

- lethal effect as high as possible;

- repellent effectiveness against targeted pests and parasites, especially those known as vectors of human and animal diseases;

- Arthropods that develop through metamorphosis should show different sensitivities to arthropodicidal preparations at different stages of their development.

Therefore, destructive agents should be effective during several stages of metamorphosis, with the aim of reducing the processing number;

- the selectivity of the preparation, i.e. the effective dose for the target organisms must be significantly lower than that which is toxic for other species;

- effectiveness of the active principle against organisms resistant to other compounds.

As is known, chlorinated hydrocarbons accumulate in living organisms. Therefore, the use of these compounds is prohibited in most countries of the world. Organophosphorus acid esters and carbamates have good effectiveness, they accumulate to a lesser extent, but they are not selective, i.e. they are also toxic to warm-blooded animals. A high degree of resistance to them also appears.

Pyrethroids, i.e. synthetic analogues of pyrethrin I contained in the flower heads of Chrysanthemum cinerariefolium have proven to be the most suitable agents for killing or controlling the above Arthropoda orders, i.e. animal lice (Phtiraptera), holometabolic insects with one pair of membrane wings (Diptera), fleas (Siphonaptera ) and the mite (Acarina).

These compounds, which usually contain two, three or four asymmetric centers, have four, eight or sixteen isomers of different spatial arrangements. Such compounds are, for example, permethrin, tetramethrin (2 asymmetric centers, 4 possible isomers), cypermethrin, cyphenothrin, cyfluthrin or decamethrin (3 asymmetric centers, 8 possible isomers) and tralometrin (4 asymmetric centers, 16 possible isomers). (In the structural formulas (1)-(23), the position of the asymmetric centers is marked with an asterisk.) The configuration of the isomers is described according to M. Elliot et al. (J. Chem. Soc., Perkin. Trans. 1, (1974) 2470-2474). The absolute configuration of the carbon atom in position l of the cyclopropane ring and the relative configuration of the carbon atom in position 3 are shown, and the configuration of the carbon atom in the ester bond (α) is defined, if it is an asymmetric center. The position of substituents on additional asymmetric centers - if they exist - is optional. These isomers with different configurations proved to be absolutely different in their arthropodicidal efficacy, metabolic properties and mammalian toxicity. Therefore, one of the main directions in the development of pyrethroids is the appropriate selection of isomers of known molecules suitable for protection against different groups of harmful organisms.

Based on the studies of insects known from the literature, a general conclusion can be made that cis-isomers of pyrethroids are more active than trans-isomers, but the effectiveness of cis-isomers also shows great differences regarding the target species. A further important experience consists in the fact that cis-isomers are at the same time more toxic to warm-blooded creatures.

According to the above, cis-isomers or mixtures rich in cis-isomers exist on the market. Such isomeric mixtures or isomers are alphamethrin [a mixture of isomers (1R-cis)αS and (1S-cis)αR cypermethrin]: (lambda-cyhalothrin/(a mixture of isomers (1R-cis)αS and (1S-cis)αR) or deltamethrin [(1R-cis)αS]. These preparations often cause irritation of the skin and mucous membranes in humans and domestic animals. The basic requirement is the selectivity of the preparations applied against ectoparasites in humans and domestic animals. Selectivity means high activity against the target organisms, and at the same time low toxicity towards warm-blooded creatures.

In our earlier studies, it was found that a mixture of (1R-cis)αS and (1S-cis)αR cypermethrin isomers in a ratio of one to one can be effectively applied in protection against harmful insects (EP-215010B1). Our results, as well as literature data, revealed a contradictory fact, according to which pyrethroids are practically inactive against herbivorous mites, but are powerful agents against ectoparasites (eg ticks or itchy mites) belonging to the order of mites.

With the knowledge of the above facts, our goal was to find more selective, and for humans and domestic animals less toxic pyrethroid isomeric mixtures or isomers suitable for killing or controlling harmful species from the point of view of public health and epidemiology, which belong to the four previously mentioned taxonomic orders. With the aim of solving this problem, we prepared isomers of the pyrethroid molecule and their various mixtures, and evaluated their effectiveness on itch mites (Psoroptes cuniculi spp.) from the order Acarina.

The table below shows data on the efficacy of cypermethrin isomers collected in house flies (Musca domestica) and itch mites (Psoroptes cuniculi).

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The relative efficacy of the 1R isomers of cypermethrin and permethrin is similar in flies and itch mites. In contrast, the 1S isomers, completely inactive in houseflies, show high efficacy against itch mites. This indicates that three of the four cypermethrin isomers are trans-isomers effective against itch mites, and two of them (1S-trans)αS and (1S-trans)αR are completely ineffective in insects and have no toxicity to warm-blooded creatures and bees.

The activity of some cypermethrin isomers and isomeric mixtures against flies and itch mites, as well as their toxicity in bees (Apis malifera) and rats, is shown in the following table:

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In order to express the harmlessness of individual isomers, the selectivity indices (flies/mites, rats/mites and bees/mites) were calculated and compared to the selectivity index of the (1R-cis)αS isomer, which shows the highest insecticidal effectiveness. Higher values indicate higher selectivity compared to the (1R-cis)αS isomer.

The (1S-trans)αS and (S-trans)αR isomers, the "transmix" and "safemix" mixtures have a suitable efficacy against itch mites, as well as a high selectivity regarding the haematotherma/itch mite ratio.

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The above biological findings confirm that the preparation according to our invention containing one or more representatives of 1S-trans, (1S-trans)αS or (lS-trans)α(R,S) isomers or racemic (1S-trans)αS(lR -trans)αR isomeric mixture of one or more compounds of the cyclopropane-carboxylic acid ester type, which contain two asymmetric centers in the cyclopropane ring and optionally one or more further asymmetric centers in the second part of the molecule, in an amount of 0.001-99 wt.%, optionally in mixtures with an amount of up to 100 wt.% of one or more auxiliary agents, primarily antioxidants, stabilizers, wetting agents, emulsifiers, dispersants, antifoam agents, diluents and/or fillers, much more selective and less toxic to humans and host animals compared to known preparations, and are much more suitable for killing or controlling harmful species, which belong to the four previously mentioned taxonomic orders. It was found that the above isomers of compounds of structural formulas (1)-(23) are preferred. Compositions containing the above isomers of compounds of structural formulas (7), (8), (9), (19), (20), (21), (22), (23) - among them primarily cypermethrin. (1S-trans) isomers and their mixtures - proved particularly advantageous. Therefore, the compositions according to our invention provide a solution to the problem previously shown in detail.

The compositions according to our invention can be prepared by methods well known in the art and can be formulated as, for example, emulsifying concentrates, microemulsions, powders or suspensions. Our invention also relates to the preparation process of 1S-trans, (1R-trans)αR, (lS-trans)αS or (lS-trans)α(R,S) isomers or racemic (lS-trans)αS/(1R- trans)αR isomeric mixtures of one or more compounds with two asymmetric centers, and in certain cases with one or more additional asymmetric centers in the cyclopropane ring, especially isomers of compounds of structural formulas (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17 ), (18), (19), (20), (21), (22), (23).

This procedure can be carried out by reaction

a) an acid chloride containing a cyclopropane ring and an alcohol containing optionally one or more asymmetric centers, or

b) an acid chloride containing a cyclopropane ring and an aldehyde containing optionally one or more asymmetric centers

and some alkali metal cyanide, and optionally second-order asymmetric transformation is applied to the reaction mixture, and their desired isomer or their mixture is isolated.

Further details of our invention are shown in the examples below, without limiting our claims.

Examples of formulation procedures

Example l

Preparation of emulsion concentrate

50.81 g of (1S-trans)α(R,S) cyphenothrin, 55.34 g of Geranol MS and 45.03 g of Geranol FF/4 were mixed and diluted to 1000 ml with xylene. The preparation is suitable for preparing emulsions for impregnating, for example, apiary frames.

Example 2

Preparation of emulsion concentrate

49.38 g of (1S-trans)α(R,S) cypermethrin, 55.88 g of Geranol MS and 35.3 g of Geranol FF/4 were mixed and diluted to 1000 ml with xylene. The preparation is suitable for preparing emulsions for impregnating, for example, apiary frames.

Example 3

Preparation of microemulsion

A mixture of 15 g of (lS-trans)α(R,S) cypermethrin, 7 g of ethoxylated-(EO=13)-propoxylated-(PO=21)-nonylphenol, 2 g of calcium linear-dodecylbenzenesulfonic acid and 12 g of POE-( 20)-sorbitan-monooleate is dissolved in a mixture of 28.6 ml of propylene glycol, 28.6 ml of boric fatty acid and 23.8 ml of sunflower seed oil, 9.5 ral of ethanol and 9.5 ml of an aliphatic hydrocarbon containing 45% naphthene. The preparation can be conveniently applied in microemulsions.

Example 4

Preparation of the powder

20 g of compound serial number 10 is added to 158 g of fine-grained perlite in a homogenizer. The mixture is then homogenized with 2 g of fatty alcohol-polyglycol ether ("G-3921" ICI"). The powder mixture is ground in an air flow mill, and 5 g of octylphenol-polyglycol ether (EO=20) is added. ("Triton X -165" Rohm&Haas) and 2 g of alkyl-sulfosuccinate ("Aerosol-13" cyanamide). Use the resulting wettable powder mixture (WP).

Example 5

Preparation of granules

60 g compound serial number 10, permethrin acid-α-cyanobenzyl ester, 1500 g polycarboxylate-alkali salt ("Sorphol", Toho), 500 g sodium salt of dodecyl-benzenesulfonic acid ("Marlon TP 370" Hüls), 500 g sucrose and 7200 g of kaolinite are mixed in a mechanical granulator, mixed with 8300 ml of water using an agitator with high crushing power (v=10 m/s) and dried in powder form. The product particle size distribution lies between 0.1 and 0.4 mm.

Example 6

Aerosol preparation

1 kg of (1S-trans)α(R,S) cypermethrin, 0.1 kg of Aerosilair 972, 0.1 kg of ethylene glycol monosalicylate, 15 kg of odorless kerosene and 50 kg of propanol are weighed into a reactor with a volume of 100 l, equipped with an agitator, and then, after dissolving, filled in cylinders with 33.3 kg of liquid propane-butane gas (25-75).

Example 7

Evaporator preparation

10 g of (lS-trans)α(R,S) cyphenothrin and 1 g of lemon flavor are dissolved in 60 ml of ethanol. The solution is used in electric vaporizers operating at 50 °C.

Chemical examples

Example 1

General procedure for the preparation of cypermethrin isomers

4.2 ml of water and 1,078 g (22 mmol) of sodium cyanide were measured in a 50 ml apparatus equipped with a magnetic stirrer. After complete dissolution, the solution was cooled to 5 °C. After the addition of 0.55 ml (0.404 g, 4 mmol) of triethylamine and 3.96 g (20 mmol) of m-phenoxybenzaldehyde, the mixture was vigorously stirred for 15 minutes, and then 4.78 g (21 mmol) of resolved permethrin chloride optical and absolute were added dropwise to the emulsion. purity above 99%, so that the temperature of the reaction mixture was maintained at 18 °C by means of external ice cooling. The mixture was reacted for 1 hour, and the resulting ester was extracted with 3 x 50 ml of ethyl acetate. The combined organic phases were washed with 50 ml of saturated sodium chloride solution, dried over magnesium sulfate and evaporated in vacuo. In this way, an average of 7.8 g of colorless oil was obtained, with two isomers in approximately equal proportions. The resulting material was chromatographed on 1 kg of silica gel using a petroleum ether mobile phase containing 5% ethyl acetate, and two diastereomers were separated. Thus, two different isomers were obtained in an average yield of 70%. The purity and identity of the product was controlled by HPLC. (Chromatograph: Waters; column: Nucleosil 5 m, Macherey-Nagel BST 250 mm x 4.6 mm; detector: UV 234 nm; mobile phase: hexane-dichloromethane-dioxane = 480-20-1). Analytical data on substances are summarized in the table below:

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Example 2

General procedure for the preparation of α-cyano-benzyl ester of permethrin acid

A method similar to that described in example 1, with the difference that 20 mmol of benzaldehyde is used instead of 20 mmol of m-phenoxybenzaldehyde.

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Example 3

General procedure for the preparation of α-cyano-(3-bromobenzyl)ester of permethrin acid

By a method similar to that described in example 1, with the difference that 20 mmol of 3-bromo-benzaldehyde is used instead of 20 mmol of m-phenoxybenzaldehyde.

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Example 4

General procedure for the preparation of α-cyano-m-phenoxybenzyl ester of 3-(2,2-dibromovinyl)cyclopropane-carboxylic acid

By a method similar to that described in example 1, with the difference that 20 mmol of racemic cis and trans chloride of 3-(2,2-dibromovinyl)-cyclopropane-carboxylic acid are used instead of 20 mmol of 3-(2,2-dichlorovinyl)-cyclopropane-carboxylic acid. acid. After column chromatography, diastereomers with higher retention were separated and then crystallized from isopropanol.

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Example 5

General procedure for the preparation of α-cyano-phenoxybenzyl ester of 3-(2,2-dimethylvinyl)-cyclopropane-carboxylic acid (cyphenothrine isomers)

By a method similar to that described in example 1, with the difference that 20 mmol of racemic cis and trans chloride of 3-(2,2-dimethylvinyl)-cyclopropane-carboxylic acid are used instead of 20 mmol of 3-(2,2-dichlorovinyl)-cyclopropane-carboxylic acid. acid. The crude product was chromatographed on 250 g of silica gel, without diastereomer separation, using a mobile phase containing 2% ethyl acetate.

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Example 6

Preparation of a crystalline product containing cypermethrin (1R-trans)αR and (1S-trans)αS isomers in a ratio of 1:1

By a method similar to that described in Example 1, trans-cypermethrin was prepared using trans-permethrin acid chloride. The ester consisting of four stereoisomers was recrystallized from a fivefold amount of methanol. The resulting material was chromatographed using a method similar to that described in Example 1. Diastereomeric fractions of higher apolarity (containing one-to-one ratio of (1R-trans)αR and (1S-trans)αS isomers) were collected and matched. Thus, after the first separation, 3 g of snow-white crystalline material was obtained. By recrystallization of the crude product, a material of purity above 99% was obtained. Serial number: 29. Melting point: 73.4 °C.

Example 7

General procedure for the preparation of cis and trans permethrin

4 g (20 mmol) of m-phenoxybenzyl alcohol and 4.78 g (21 mmol) of resolved cis and trans permethrin acid chloride were weighed in a 50 ml apparatus equipped with a magnetic stirrer. The mixture was reacted in vacuo at 70 °C for 4 hours, the resulting ester was diluted with 50 ml of ethyl acetate, and washed with 50 ml of a 5% sodium bicarbonate solution, and then washed with 50 ml of a saturated sodium chloride solution, dried over magnesium sulfate and evaporated in vacuo. 7.8 g of white crystalline substance was obtained.

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Example 8

General procedure for preparing a mixture of cypermethrin isomers (1S-trans)αS, (1S-trans)αR ("safemix")

Using a method similar to that described in example 1, with the difference that resolved 1S-trans permethrin acid of optical and absolute purity above 99% was used as the starting material, and the product was isolated immediately after extraction, without chromatography, 8.0 g of colorless oil containing 1S-transS and 1S-transR isomers in the ratio. 47:53, as demonstrated by HPLC.

Example 9

General procedure for the preparation of the (1S-trans)αR isomer of the α-cyanobenzyl ester of permethrin acid using a second-order asymmetric transformation

Using a method similar to that described in example 8, with the difference that the isolated product was dissolved in five times the amount of isopropanol, with the use of 0.4 equivalents of triethylamine base, and after dissolution and inoculation with the pure 1S-transR isomer, it was then gradually cooled and turned into a suspension containing only crystals of the 1transR isomer. The resulting material was filtered, washed with acetic acid containing isopropanol and dried. 7 g of snow-white crystalline material, identical to product number 10, was obtained. Purity according to HPLC: 98%.

Example 10

General procedure for the preparation of p-methylbenzyl ester of trans-permethrinic acid

20 mmol of p-methylbenzyl alcohol, 50 ml of dry benzene, 20 mmol of pyridine were weighed into a 50 ml reactor equipped with a magnetic stirrer. The mixture was cooled to 2 °C using an external ice bath, and then with a gradual increase and maintaining the temperature at 5-10 °C, 4.78 g (21 mmol) of trans-permethric acid chloride was added. The mixture was then left to react for half an hour. The resulting ester was diluted with 50 ml of benzene and washed with 50 ml of 1% hydrochloric acid solution, 50 ml of 5% sodium bicarbonate solution and then with 50 ml of saturated sodium chloride solution, dried over magnesium sulfate and evaporated in vacuo. The crude product was recrystallized from hexane. 4.5 g of white crystalline material was obtained. Purity according to HPLC: 98%. Melting point: 57-59 °C. Serial number: 37.

Example 11

General preparation procedure of (1S-trans)αS, (1S-trans)αR isomeric mixture of α-ethynyl-m-phenoxybenzyl ester of chrysanthemum acid

Using a method similar to that described in procedure 10, with the difference that the alcohol component was α-ethynyl-m-phenoxybenzyl alcohol, the product was prepared after washing and evaporation. 7.5 g of colorless oil was obtained. Purity according to HPLC: 96.5 %. Serial number: 38.

Biological examples

The numbering of the isomers was the same as in the chemical examples.

Example 1

Efficacy testing

A laboratory strain of Psorptes cuniculi, a common parasite in rabbits that causes itchy ears, was used to study the effectiveness of the preparation. Test solutions were prepared in distilled water, using ethanol as a co-solvent (max. 5%) and Tween 80 detergent (0.2%). Mite exposure was carried out in ELISA plate units. 80 ml of the prepared solution was poured into the ELISA plate units, and then 5 mature mites were placed in each unit using a fine brush. For each compound, at least 5 concentrations were tested in 4-6 parallel tests, with repetition 2-3 times in the concentration range 250-500-1000-2000 ppm. Control animals were treated only with co-solvent and detergent. No mortality occurred in the control group. After processing, the panels were placed on a 10 l container, with a relative humidity of 70%, achieved using a salt solution. The container was then placed in a thermostat set to 25 °C. After 48 hours, dead organisms were counted. The effectiveness of the compounds was characterized by the smallest concentration that caused 100% mortality (MIC - minimum inhibitory concentration).

α-cyano-m-phenoxybenzyl esters of 3-(2,2-dichlorovinyl)-cyclopropane-carboxylic acids, cypermethrin isomers (chemical example 1)

serial number isomers MIC (ppm)

1 (1S-trans)αS 250

2 (1S-trans)αR 250

3 (1R-trans)αR >2000

4 (1R-trans)αS 250

5 (1R-cis)αR >2000

6 (1R-cis)αS 250

7 (1S-cis)αS >2000

8 (1S-cis)αR >2000

1+2 (1S-trans)αS+(1S-trans)αR 250

1+3 (1S-trans)αS+(lR-trans)αR 250

2+4 (lS-trans)αR+(lR-trans)αS 250

5+7 (1R-cis)αR+(1S cis)αS >2000

6+8 (lR-cis)αS+(lS-cis)αR 250

1-8 cypermethrin 500

α-cyanobenzyl esters of permethrin acid (chemical example 2)

serial number isomers MIC (ppm)

9 (1S-trans)αS 1000

10 (1S-trans)αR 1000

11 (1R-trans)αR >2000

12 (1R-trans)αS 1000

13 (1R-cis)αR >2000

14 (1R-cis)αS >2000

15 (1S-cis)αS >200

16 (1S-cis)αR >2000

α-cyano-(3-bromobenzyl)-ester of permethrin acid (chemical example 3)

serial number isomers MIC (ppm)

17 (1S-trans)αS 500

18 (1S-trans)αR 1000

19 (1R-trans)αR >2000

20 (1R-trans)αS 1000

21 (1R-cis)αR 1000

22 (1R-cis)αS >2000

23 (1S-cis)αS >2000

24 (1S-cis)αR >2000

α-cyano-m-phenoxybenzyl esters of 3-(2,2-dibromovinyl)-cyclopropane carboxylic acid (chemical example 4)

serial number isomers MIC (ppm)

25 (lR-cis)αS+(lS-cis)αR >2000

26 (lR-trans)αS+(1S-trans)αR 500

α-cyano-m-phenoxybenzyl esters of 3-(2,2-dimethylvinyl)-cyclopropane-carboxylic acid (chemical example 5)

serial number isomers MIC (ppm)

27 cis isomer >2000

28 trans isomer 500

27+28 Cyphenothrin 1000

permethrin isomers (chemical example 7}

serial number isomers MIC (ppm)

30 1S-cis >2000

31 1R-cis >2000

32 1R-trans 500

33 1S-trans 1000

34 cis isomers >2000

35 trans isomers 500

36 permethrin 500

Example 2

Speed of effect

The rate of the killing effect was determined by the same method as that described in biological example 1, with the difference that mortality was also assessed after 28, 48 and 72 hours from the start of exposure. The obtained results are shown in the following table.

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Claims (11)

1. Arthropodicidal ectoparasiticidal composition, characterized in that it contains one or more representatives of 1S-trans, (lS-trans)αS or (1S-trans)α(R,S) isomers or racemic isomeric mixture (1S-trans)αS(1R -trans)αR of one or more compounds of the cyclopropane-carboxylic acid ester type, which contain two asymmetric centers in the cyclopropane ring and optionally one or more further asymmetric centers in other parts of the molecule, in an amount of 0.001-99 wt. %, optionally mixed with up to 100 wt. % of one or more auxiliary agents, preferably antioxidants, stabilizing reagents, wetting agents, emulsifying agents, dispersing agents, antifoaming agents, diluents and/or fillers. 2. The composition according to claim 1, characterized in that it contains one or more representatives of the 1S-trans, (1S-trans)αS or (lS-trans)α(R,S) isomer or a racemic isomeric mixture (lS-trans)αS( lR-trans)αR of one or more compounds of structural formulas (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) , (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), ( 23), in the amount of 0.001-99 wt. %, optionally mixed with up to 100 wt. % of one or more auxiliary agents, preferably antioxidants, stabilizing reagents, wetting agents, emulsifying agents, dispersing agents, antifoaming agents, diluents and/or fillers. 3. A composition that is active against ectoparasitic arthropods belonging to the order of mites (Acarina) according to claim 1, characterized in that it contains one or more representatives of 1S-trans, (1S-trans)αS or (1S-trans)α(R,S ) isomer or racemic isomeric mixture (1S-trans)αS(lR-trans)αR of one or more types of cyclopropane-carboxylic acid ester compounds, which contain two asymmetric centers in the cyclopropane ring and optionally one or more further asymmetric centers in other parts of the molecule, in the amount of 0.001-99 wt. %, optionally mixed with up to 100 wt. % of one or more auxiliary agents, preferably antioxidants, stabilizing reagents, wetting agents, emulsifying agents, dispersing agents, antifoaming agents, diluents and/or fillers. 4. A composition that is active against ectoparasitic arthropods belonging to the order of animal lice (Phthiraptera) according to claim 1, characterized in that it contains one or more representatives of lS-trans, (1S-trans)αS or (lS-trans)α(R, S) isomer or racemic isomeric mixture (1S-trans)αS(lR-trans)αR of one or more compounds of the cyclopropane-carboxylic acid ester type, containing two asymmetric centers in the cyclopropane ring and optionally one or more further asymmetric centers in other parts of the molecule , in the amount of 0.001-99 wt. %, optionally mixed with up to 100 wt. % of one or more auxiliary agents, preferably antioxidants, stabilizing reagents, wetting agents, emulsifying agents, dispersing agents, antifoaming agents, diluents and/or fillers. 5. A composition that is active against ectoparasitic arthropods belonging to the order of holometabolic insects with one pair of membranous wings (Diptera), characterized by the fact that it contains one or more representatives of lS-trans, (1S-trans)αS or (lS-trans)α( R,S) isomer or racemic isomeric mixture (lS-trans)αS(lR-trans)αR of one or more compounds of the cyclopropane-carboxylic acid ester type, containing two asymmetric centers in the cyclopropane ring and optionally one or more further asymmetric centers in the other parts of the molecule, in the amount of 0.001-99 wt. %, optionally mixed with up to 100 wt. % of one or more auxiliary agents, preferably antioxidants, stabilizing reagents, wetting agents, emulsifying agents, dispersing agents, antifoaming agents, diluents and/or fillers. 6. A composition that is active against ectoparasitic arthropods belonging to the order of fleas (Siphonaptora), characterized by the fact that it contains one or more representatives of 1S-trans, (1S-trans)αS or (1S trans)α(R,S) isomers or racemic isomeric mixture (1S-trans)αS(lR-trans)αR of one or more types of cyclopropane-carboxylic acid ester compounds, containing two asymmetric centers in the cyclopropane ring and optionally one or more further asymmetric centers in other parts of the molecule, in the amount of 0.001 -99 wt. %, optionally mixed with up to 100 wt. % of one or more auxiliary agents, preferably antioxidants, stabilizing reagents, wetting agents, emulsifying agents, dispersing agents, antifoaming agents, diluents and/or fillers. 7. Composition according to claim 1, characterized in that it contains one or more representatives of 1S-trans, (1S-trans)αS or (1S-trans)α(R,S) isomers or racemic isomeric mixture (1S-trans)αS( lR-trans)αR of one or more compounds of structural formulas (7), (8), (9), (19), (20), (21), (22), (23), in the amount of 0.001-99 mass . %, optionally mixed with up to 100 wt. % of one or more auxiliary agents, preferably antioxidants, stabilizing reagents, wetting agents, emulsifying agents, dispersing agents, antifoaming agents, diluents and/or fillers. 8. The method of preparing an arthropodicidal ectoparasitic composition according to claim 1, characterized in that one or more representatives of the 1S-trans, (1S-trans)αS or (lS-trans)α(R,S) isomers or a racemic isomeric mixture (1S- trans)αS(lR-trans)αR of one or more types of cyclopropane carboxylic acid ester compounds, containing two asymmetric centers in the cyclopropane ring and optionally one or more further asymmetric centers in other parts of the molecule, in an amount of 0.001-99 wt. % are mixed with an amount of up to 100 wt.% of one or more auxiliary agents, preferably antioxidants, stabilizing reagents, wetting agents, emulsifying agents, dispersing agents, antifoaming agents, diluents and/or fillers. 9. The method according to claim 8, characterized in that an emulsifying concentrate or microemulsion is prepared. 10. A method of killing ectoparasitic arthropods, characterized in that an effective amount of the composition according to claim 1 is applied to said arthropods or their environment or their habitats, at once or several times. 11. Method of preparing one or more representatives of 1S-trans, (1S-trans)αS or (lS-trans)α(R,S) isomers or a racemic isomeric mixture (1S-trans)αS(lR-trans)αR of one or more of the type of cyclopropane-carboxylic acid ester compounds, which contain two asymmetric centers in the cyclopropane ring and optionally one or more further asymmetric centers in other parts of the molecule, characterized by the fact that they react a) some acid chloride containing the corresponding cyclopropane ring and some aldehyde containing optionally one or more asymmetric centers, or b) some acid chloride containing the corresponding cyclopropane ring and some aldehyde containing optionally one or more asymmetric centers and some alkali metal cyanide, and optionally applying some second-order asymmetric transformation to the reaction mixture, and isolating the desired isomer or their mixture.