NL7907888A - NEW CYCLOPROPAN CARBOXYLATES, METHOD FOR PREPARING THESE COMPOUNDS, AND INSECTICIDE AND / OR ACARICIDE PREPARATIONS CONTAINING SUCH A COMPOUND. - Google Patents

Description

* Ίίύ '49 358 / Bos / AS 1

Novel cyclopropane carboxylates, method of preparing these compounds, as well as insecticidal and / or acaricidal preparations containing such a compound.

The invention relates to new cyclopropanecarboxylates, their preparation and insecticidal and / or acaricidal compositions containing these compounds as an active ingredient.

The new compounds according to the invention have the formula 1 of the formula sheet, wherein R 1 and R 2, which may be the same or different, are each a hydrogen or halogen atom or a methyl group, A an oxygen or sulfur atom or a methylene group 10 R is an oxygen atom or a group of the formula

-CH = CH-, R4 is a hydrogen atom or an ethynyl or cyano group, and (a) Rg is a group of formula 2 or 3 of the formula sheet, wherein Rg is a halogen atom when A is an oxygen or sulfur atom and R represent a group of the formula -CH = CH-, when A

a methylene group, R a group with the -CH = CH- and R4 represent a hydrogen atom, or when A represents a methylene group, R represents an oxygen atom and R ^ represents a hydrogen atom or an ethynyl group, or (b) when A represents a methylene group, R a group of the formula -CH = CH- and R ^ represent an ethynyl group, Rg is a group of formula 4 of the formula sheet, wherein Rg is a hydrogen atom or a methyl group, where when Rg is a hydrogen atom, R ^ is a group of the formula 5 or 25 6 of the formula sheet (wherein Rg represents a halogen atom or a methyl or methoxycarbonyl group and Rg represents a halogen atom or a methyl group) and when Rg is a methyl group, R ^ is a methyl group, or (c) when A is a methylene group and R4 represents a cyano group, Rg is a group of the formula 7 of the formula sheet, wherein R 1 represents a hydrogen atom or a methyl group, where, when R 1 is a hydrogen atom, R 1; is a group of the formula 8 or 6 of the formula sheet (where R 1 represents a halogen atom or a methyl, methoxy, carbon 2 or methoxymethyl group and R 5 represents hydrogen or halogen atom or a methyl group) and when a methyl group is R 1 is a methyl group.

The meaning of the aforementioned halo-5 atom is that of a chlorine or bromine atom or for the groups R 1 and R 2 and a chlorine, bromine or fluorine atom for the groups R 1, Rg and Rg.

An object of the invention is to provide an inexpensive insecticide and acaricide that has low mammalian toxicity and exhibits a strong insecticidal effect when used for environmental hygiene, agriculture and household horticulture.

Among the insecticides commonly used, pyretrum extracts (containing pyrethrin 15) and the synthetic alletrine, which is a homolog of the active ingredient of pyrethrum extracts, include the insecticides which have a rapid effect and are non-toxic to mammals and therefore can be applied without any fear. However, the use of pyretrum-20 extracts tends to a limited size because it is relatively expensive, despite its excellent utility.

Many carboxylates were synthesized by the applicant and their biological activity investigated. As a result, the esters of formula I have been found to have excellent insecticidal activity not only against insects which are harmful to general hygiene such as flies, but also insects which are harmful to agricultural crops, in particular the green rice leaf beetle (Nephotettix cincticeps ), diamondback moth (Plutella xylostella), swarmworms ("armyworms") and cutworms. It has further been found that the esters are effective against mites and have low mammalian toxicity and can be prepared at a low cost. This led to the present invention.

The insecticides of the invention have a wide range of applications in the prevention of epidemics. However, they are also excellent insec 790 7 8 68 3 *. Since they have a ticidal effect and residual effect against insects that are harmful to stored grains, agricultural crops, trees in forests or forests and pets, they are very useful for controlling these insects.

In particular, because of their low toxicity, they can be used for crops for harvesting, greenhouse cultivation, household horticulture and food packaging materials. Examples of the insects described above are the following: 10 (1) General hygiene:

Mosquitoes, (e.g. Culex pipiens molestus,

Culex pipiens pallens, Aedes aegypti,

Anopheles Stephens!).

Flying, (for example, Museums domestica, Lucilla caesar, 15 Boettcherisca peregrina).

Cockroaches, (e.g. Periplaneta americana, P. fulginosa, Blattella germanica).

Mosquitoes, (for example, Prosimulium hirtipes, Simulium aokii).

20 Fleas, (for example Pulex irritans).

Lice, (e.g. Pedimulus humanus, Phthirus pubis).

(2) Stored crops:

Coleoptera (e.g. Sitophilus zeamais,

Tribolium castaneum, Tenebrio molitor).

Lepidoptera (for example, Ephestia cautella).

Acarina (for example, Tyrophagus dimidiatus).

(3) In the rice field:

Hemiptera;

Delphacidae (plant beetles, delphacids) (for example Sogatella fureifera, Nilaparvata lugens, Laodelphax striatellus).

Deltccephalidae (leaf beetles) (e.g. Nephotettix cinditiceps, Tettigella viridis).

Aphididae (aphids) (for example Rhopalosiphum 35 rufiabdominalis, Rhopalosiphum padi).

Pentatomidae (scabies, scale insects) (e.g. Nezara antennata, Leptocorixa corbetti).

Lepdoptera (moths and butterflies) (eg Chilo 790 7 8 88 r 4 suppressalis / Craphalocrocis medinalis, Sesamia inferens, Parnara guttata).

(4) Vegetables, fruit trees, forests:

Lepidoptera (e.g. Plutella xylostella, 5 Spodoptera litura, Spodoptera exigua,

Marnestera brassicae, Leucania separata, Ostrinia nubilalis, Pieris rapae,

Papilio xuthus).

Hemiptera (for example, Myzus persicae, Apis gossypii).

10 Coleoptera (beetles (e.g. Phaedon brassicae).

Diptera (flies) (e.g. Hylemya platus,

Hylemya antiqua).

Isoptera (termites) (for example, Coptotermes formosanus, Leucotermes speratus).

Tetranychidae (spider mites) (for example, Tetranychus cinnavarinus, T. ulticae, T. kanzawai, Panonychus citri, P. ulmi, Aculus pelekassi).

(5) In the forest:

For example, Dendrolimus spectabilis, 20 Monochamus alternatus, Archips fumiferana,

Oligonychus hondoensis.

(6) Livestock:

For example, Boophilus microplus.

The eyelopropane carboxylates according to the invention are new compounds and were first synthesized by the applicant. The synthesis of these compounds will now be explained in more detail.

The carboxylates of the formula 1 are obtained by doing an alcohol or its halide of the formula 9 of the formula sheet, wherein R 11, A, R and have the same meanings as mentioned above and X is a hydroxyl group or a halogen atom reacting with a carboxylic acid of formula 10 of the formula sheet, wherein R 1 has the same meaning as mentioned above, or a reactive derivative thereof, in the presence of a suitable reaction aid, if necessary. The reactive derivative referred to herein means 7Ω n 7Q fifi 5, * acid halides, acid anhydrides and alkali metal or organic tertiary base salts of the acid.

Also, the carboxylate of the formula 1, wherein the group is a cyano group, can be obtained by reacting an aldehyde of the formula 11 of the formula sheet, wherein R 1, R 2, A and R have the same meanings as mentioned above with a carboxylic acid halide of the formula 12 of the formula sheet, wherein Rg has the same meaning as mentioned above and Y10 is a halogen atom, and an alkali metal cyanide.

These synthetic methods will now be discussed in more detail.

First, there is mentioned a case where the group X in formula 9 is a hydroxyl-15 group. In this case, the esters of the formula 1 are obtained by reacting an alcohol of the formula 13 of the formula sheet, wherein R 1, R 2, A, R and R 1 have the same meanings as mentioned above, with a carboxylic acid of the formula 10 or its acid halide or acid anhydride.

When the carboxylic acid is used, the reaction is run under dehydrating conditions. That is, the esters of the formula 1 can be obtained by reacting an alcohol of the formula 13 with a carboxylic acid of the formula 10 at Λ Λ -30 to 100 ° C for 0.5 to about 20 hours in a solvent (e.g. benzene, toluene, xylene or mixtures thereof) in the presence of a dehydrating agent or condensing agent (e.g. dicyclohexyl-30 carbodiimide).

When the acid halide is used, the object is sufficiently achieved even at room temperature by reacting an alcohol of formula 13 with the acid halide using an organic tertiary base (eg pyridine or triethylamine) as an acid binding agent.

The acid halide used in this reaction is not particularly limited, but an acid chloride is generally used. In this reaction, the use of a solvent is beneficial in order to smooth the reaction 790 7 8 88 y 1 6 and generally inert solvents such as benzene, toluene, xylene, ether, hexane and heptane are used. The reaction temperature is -30 ° to 100 ° C and the reaction time is 0.5 to 10 hours.

When the acid anhydride is used, the object is achieved by reacting an alcohol of the formula 13 with the acid anhydride at -20 ° to 100 ° C without special reaction aids.

The use of a solvent (eg benzene, toluene, xylene, hexane or acetone) is beneficial to smooth the reaction, but is not essential.

Secondly, a case is given in which the group X in formula 9 is a halogen atom.

In this case, the esters of the formula I are obtained by reacting halides with carbon black the formula 14 of the formula sheet, wherein R 1, R 2, A, R and R 1 have the same meanings as mentioned above and Z is a halogen atom with an alkali metal salt or organic tertiary base salt of the carboxylic acid of formula 10.

When the organic tertiary base is ethyl amine or triethylamine, the intended esters can be obtained by converting a carboxylic acid of the formula 10 into a salt with the base in an inert solvent (eg benzene, toluene, acetone or dioxane) and then reacting the obtained salt with a halide of the formula 9 at 0 ° to 150 ° C for 0.5 to 10 hours.

When the alkali metal salt is used, the intended esters can be obtained by carrying out the reaction at 0 ° to 150 ° C for 0.5 to 20 hours in a 2-phase system consisting of an inert solvent (eg benzene, toluene, xylene or heptane) and water using 1 to 10 mol% of a phase transfer catalyst such as tetra-n-butylammonium bromide or benzyltriethylammonium chloride.

The group Z in the formula 14 is not particularly limited, but is generally a chlorine or bromine atom.

790 7 8 88 7 *

Thirdly, a case is given in which an aldehyde of the formula II is reacted with a carboxylic acid halide of the formula 12 and an alkali metal cyanide. When the reaction is carried out in a non-aqueous system comprising an inert solvent, "crown ethers" are used as the catalyst. When the reaction is conducted in a 2-phase system comprising an inert solvent and water, phase transfer catalysts such as 10 organic quaternary ammonia salts are used. used. In either case, the intended compounds can be obtained in a high yield.

The alkali metal cyanide used in the reaction includes sodium cyanide and potassium cyanide. The inert solvent includes aromatic hydrocarbons (eg benzene, toluene and xylene), aliphatic hydrocarbons (eg hexane, heptane and octane), halogenated aromatic hydrocarbons (eg chlororforzene) and halogenated aliphatic hydrocarbons (eg methylene dichloride, chloroform and carbon tetrachloride) ). For example, the term "crown ethers" refers to large ring pore eaters such as dibenzc-18-crown-6 and dicylohexyl-18-crown-6.

The organic quaternary ammonium salt includes benzyl triethylammonium chloride, tetra-n-butyl ammonium bromide and the like. The amount of the catalyst is generally 1 to 10 mol%. The objectives of the reaction can be achieved at -10 ° to 50 ° C in 0.5 to 20 hours.

Examples of the synthesis will now be given using a standard procedure.

(a) Method by reaction between alcohol and carboxylic acid halide.

0.05 mol of the alcohol is made up in three times the volume of dry benzene and 0.075 mol of pyridine is added thereto. 0.053 mol of the carboxylic acid chloride is made up in three times the volume of dry benzene and added dropwise, 790 7 8 55

X

8 at 5 ° C or less, the above solution under stirring and cooling is ice. After the addition is complete, stirring is continued overnight at 25 ° C.

A little water is added to the reaction solution to dissolve the deposited pyridine hydrochloride, followed by phase separation. The organic layer is washed with 5% aqueous hydrochloric acid, saturated sodium bicarbonate solution and then 10 with saturated sodium chloride solution, dried over anhydrous sodium sulfate and freed from the solvent by evaporation. The resulting residue is purified by colochormatography on silica gel to obtain the intended ester.

(B) Method by reaction between alcohol and carboxylic anhydride.

0.05 mol of the alcohol is dissolved in three times the volume of toluene and 0.05 mol of the carboxylic anhydride is added thereto. After stirring for three hours at room temperature, the reaction mixture is heated to reflux for 1 hour, cooled and then extracted with 5% aqueous sodium hydroxide solution to transfer the carboxylic acid by-product to the aqueous layer. The organic layer is washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate and freed from the solvent by evaporation. The resulting residue is purified by column chromatography on silica gel to obtain the intended ester.

(c) Method by reaction between alcohol and carboxylic acid.

0.05 mol of the alcohol and 0.05 mol of the carboxylic acid are dissolved in three times the volume of dry benzene and 0.08 mol of dicyclohexylcarbodiimide is added thereto. After stirring overnight at 25 ° C, the reaction solution is filtered to remove dicyclohexylurea and the filtrate is evaporated. The resulting residue is purified by 790 7 8 88 t * 9 by column chromatography on silica gel to obtain the intended ester.

(d) Method by reaction between alcohol halide and organic tertiary base salt of carboxylic acid.

0.05 mol of a halide of the alcohol and 0.06 mol of the carboxylic acid are dissolved in three times the volume of acetone. Also, 0.08 mol of triethylamine is dissolved in three times the volume of acetone 10 and is added dropwise to the above solution at 15 ° to 20 ° C with stirring. After the addition is complete, the reaction solution is refluxed for 2 hours, then cooled and filtered to remove the deposited triethylamine hydrochloride. After removal of acetone from the filtrate by evaporation, the residue is added to three times the volume of benzene and in the same manner as in the standard method (a), the resulting organic layer is washed, dried, evaporated and chromatographed on a column with silica gel to give the arc ester.

(e) Method by reaction between alcohol halide and alkali metal salt of carboxylic acid.

0.05 mol of the halide and 0.055 mol

of the sodium salt of the carboxylic acid are dissolved in four times the volume of toluene and three times the volume of water, respectively. Both solutions are mixed and 1.3 moles of tetra-n-butylammonium bromide 30 are added thereto. After stirring at 70 ° to 80 ° C

the reaction solution is allowed to cool for 4 hours, then it is washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate and then the solvent is removed by evaporation.

The obtained residue is purified by column chromatography on silica gel to obtain the intended ester.

(f) Method by reaction between aldehyde, alakali metal cyanide and carboxylic acid halide.

79078 88 10 (f-1) 0.075 mol of sodium cyanide and 0.8 g of dibenzo-18-crown-6 are suspended in 100 ml of dry benzene. Also, 0.05 mol of the aldehyde and 0.0525 mol of the carboxylic acid chloride are dissolved in 50 ml of dry benzene and this is added dropwise to the above suspension at room temperature with stirring. After the addition is complete, stirring is continued overnight at 25 ° C. The reaction solution is washed with a saturated sodium chloride solution and freed from the solvent by evaporation. The residue is purified by column chromatography over silica gel to obtain the intended ester.

(f-2) 0.075 mol of sodium cyanide and 2.5 mol of tetra-n-butylammonium bromide are dissolved in 20 ml of water. Also, 0.05 mol of the aldehyde and 0.0525 mol of the carboxylic acid chloride are dissolved in 40 ml of toluene and this is added dropwise to the above solution at 25 ° C over 3 hours with stirring. After the addition is complete, stirring is continued for 3 hours. The reaction solution is washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate and then freed from the solvent by evaporation. The residue is purified by column chromatography over silica gel to give the intended ester.

Typical examples of the cyclopropane carboxylates of the formula 1 of the invention are listed in Table A, but these esters are of course not limited to these examples.

The esters of Formula 1 include stereoisomers due to the steric configuration of the carboxylic acid and optical isomers due to asymmetric carbon atoms on the carboxylic acid and alcohol, but all of these isomers are included within the scope of the present invention.

Table A.

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φ tn φ μφ ®® ® S

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The aldehydes of the formula II, new compounds used as intermediates for preparing the present compounds of the formula 1, can be prepared by the following methods.

The first is a process consisting of reacting alcohols of the formula 15, wherein R 1 A and R have the same meanings as mentioned above, with an oxidizing agent.

The alcohols of formula 15 are described in the form of formula 16 of the formula sheet, wherein R 1 and R 2, which may be the same or different, each have a halogen atom or a lower alkyl group, 15 m and h each a number of 0 to 3 and A represent an oxygen or sulfur atom in Japanese Patent Application Laid-Open No. 125523/1975. They are also described in Japanese Patent Applications Laid-Open No. 58712/1976 and 30632/1973 in the form of formulas 17 and 18 of the formula sheet, respectively.

The oxidizing agent includes manganese dioxide, chromium trioxide / pyridine, pyridinium chlorochromate, chromium trioxide / graphite, potassium chromate / sulfuric acid, lead tetraacetate / pyridine, dimethyl sulfoxide and the like.

The solvent, reaction time and reaction temperature vary with the type of oxidizing agent. In general, however, the intended aldehydes can be obtained by conducting the reaction at 20 ° to 200 ° C for 1/3 to 20 hours using a solvent such as aromatic hydrocarbons (eg benzene, toluene and xylene), halogenated the hydrocarbons (eg methylenediochloride, chloroform, carbon tetrachloride, ethylene dichloride and chlorobenzene), hexane, ether or petroleum ether.

These solvents can be used alone or in combination.

The second is a process consisting of preparing the compounds of formula 11, -n 7 Q fifi 22 in which group A is an oxygen or sulfur atom, by a thiophene halide of formula 19 of the formula sheet, which has the same meaning has as mentioned above and E is a halogen atom to react with an alkali metal salt of the aldehyde of the formula of the formula sheet wherein R2 and A have the same meanings as mentioned above or an alkali metal salt of its acetate in an inert solvent in the presence of a copper catalyst under heating.

The halogen atom E in the formula 19 includes chlorine, bromine and iodine atoms, of which bromine and iodine atoms are preferred. The copper catalyst includes copper powder, copper (I) chloride, copper (II) chloride, copper (II) bromide and the like. The solvent includes toluene, xylene, naphthalene, pyridine, nitrobenzene, dinitrobenzene, chlorobenzene, dichlorobenzene, Ν, Ν-dimethylformamide, dimethyl sulfoxide and the like. These solvents can be used alone or in combination. A reaction temperature of 100 ° to 200 ° C, preferably 120 ° to 170 ° C, and a reaction time of 1 to 30 hours are sufficient to obtain the intended aldehydes.

When the acetal is used, it must be returned to the aldehyde after the reaction by acid treatment. As the acetal, dimethyl acetal and diethyl acetal are generally used. The acid includes hydrochloric, sulfuric, nitric, acetic, formic and the like.

The third is a process consisting of preparing the compounds of the formula 11, wherein the group A is a methylene group, by an alkali metal salt of thiophene of the formula 21 of the formula sheet, wherein R 1 has the same meaning as mentioned above. and G represents an alkali metal or reacting a group of the formula MgJ, wherein J is a halogen atom with an acetal of the haloaldehyde of the formula 22, wherein R2 and R have the same meanings as mentioned above and L has a halo 790 7 8 88 23 is atom.

The alkali metal G in formula 21 includes lithium, sodium and potassium atoms. The halogen J in the group MgJ includes bromine and iodine atoms and the same 5 L in the formula 22 includes chlorine, bromine and iodine atoms.

The acetal generally includes dimethyl acetal and diethyl acetal. The solvent includes ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, pentane, hexane, heptane, benzene and the like.

These solvents can be used alone or in combination. The reaction temperature is -70 ° to 70 ° C when G is an alkali metal and -20 ° to 120 ° C when G is MgJ. This condensation reaction comes to an end within 0.5 to 20 hours and the resulting acetal is recycled to the aldehyde in the same manner as above to obtain the intended compound.

The fourth is a process consisting of preparing the compounds of formula 11, wherein -20 in the group A is a methylene group, by a halomethyl derivative of thiophene of the formula 23 of the formula sheet, which has the same meaning as above and Q is a halogen to react with a Grignard reagent of a haloaldehyde hydacetal of the formula 24 of the formula sheet wherein R2 and R have the same meanings as mentioned above and J is a halogen. "

The halogen atom J in the formula 24 includes chlorine, bromine and iodine atoms and the same Q in the formula 24 generally includes bromine and iodine atoms.

The acetal is generally dimethyl acetal or diethyl acetal. The reaction solvent is the same as described in the third method. This reaction comes to an end at -20 ° to 120 ° C in 0.5 to 20 hours and after the reaction, the resulting acetal is recycled to the aldehyde to obtain the target compound.

In the third and fourth methods, using a catalyst can make the reaction run smoothly, but this is not always essential. The cat 790 7 8 88 24

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lysator includes silver bromide, copper (II) chloride, chromium trioxide and the like, and the amount thereof is preferably 0.1 to 10%.

The preparation of the aldehydes of formula 11 will be illustrated by the following preparation examples, but the invention is not limited to these examples.

(1) 3- (3-thienyloxy) benzaldehyde.

20.6 g of 3- (3-thienyloxy) benzyl alcohol, 26.1 g of manganese (IV) oxide and 100 ml of chloroform were mixed and heated under reflux for 3 hours.

After cooling to room temperature, the reaction solution was filtered through a pad of celite which was then carefully washed with 200 ml of chloroform. The filtrate and washings were combined and washed with 30 ml of 10% aqueous hydrochloric acid and then with 30 ml of saturated sodium chloride solution. The chloroform layer was then dried over magnesium sulfate and the chloroform was evaporated. The resulting residue was distilled in vacuo (bp 108-113 ° C / 0.4 mm

Hg) to obtain 19.1 g of a colorless liquid (yield 93.6%).

(2) 3- (2-thienyloxy) benzaldehyde.

4.0 g of 66.5% sodium hydride diluted with nujol 25 was freed from the nujol by washing with n-hexane and then 80 ml of pyridine was added thereto. 14.7 g of 3-hydroxybenzaldehyde was added to the solution over 20 min under ice-cooling, followed by stirring at 25 ° C for another 30 min. Then, 16.3 g of 2-bromothiophene and 1.0 g of copper (I) chloride was added and after displacement with nitrogen gas, the mixture was heated to reflux for 15 hours.

After cooling to room temperature, the reaction solution was poured into 300 ml of ice water containing 100 ml of concentrated hydrochloric acid and extracted with two 200 ml portions of ether. The ether layer was washed with two 100 ml. Portions of 10% aqueous hydrochloric acid, 50 ml of saturated sodium bicarbonate solution and then with 50 ml of saturated sodium chloride solution and dried over 790 7 8 88 25% magnesium sulfate. After evaporation of the ether, the resulting residue was distilled in vacuo (bp 98-104 ° C / 0.2 mm Hg) to obtain 8.3 g of a colorless liquid (yield 40.7%).

5 (3) 3- (2-thenyl) benzaldehyde.

To a Gignard solution prepared from 19.6 g of 2-bromothiophene and 3.2 g of magnesium in 80 ml of ether, 1.0 g of copper (I) oxide was added. After displacement with nitrogen gas, a solution of 22.9 g of 3-chloromethyl-benzaldehyde diethyl acetal in 40 ml of ether was added dropwise thereto over 1 hour under ice-cooling. After the addition was complete, the solution was refluxed for 2 hours. After cooling to room temperature, the reaction solution was poured into 150 ml of ice water containing 10 g of ammonium chloride and extracted with two 100 ml portions of ether. The ether layer was washed with 40 ml of water and dried over magnesium sulfate. After evaporation of the ether, the resulting residue was distilled in vacuo (bp 117-123 ° C / 0.12 mm Hg) to give 19.0 g of a colorless liquid (yield 68.8%).

This product was 3-2-thenyl) benzaldehyde diethyl acetal.

This acetal (10.0 g) was added to a mixed solvent from 100 ml 5% aqueous hydrochloric acid, 30 ml toluene and 30 ml tetrahydrofuran, followed by stirring at 25 ° C for 15 hours. After phase separation, the aqueous layer was extracted with 100 ml of toluene.

The organic layers were combined, washed with 30 ml of saturated sodium bicarbonate solution and then with 30 ml of saturated sodium chloride solution and dried over magnesium sulfate. The solvent was evaporated to obtain 6.9 g of a colorless liquid (yield 94.2%).

(4) 5- (3-thenyl) furfural.

A solution of 16.3 g of 3-bromothiophene in 40 ml of ether was cooled to -70 ° C or less after displacement with nitrogen gas and 69 ml of an n-hexane solution containing 1.6 mol / 1 n-butyl lithium, was added dropwise thereto over 2 hours. The 79078 88 <. . The mixture was stirred at -70 ° C for an additional 30 min. Then, 31.2 g of a toluene solution containing 70% 5-chloromethylfurfuraldiethylacetal was dissolved in 70 ml ether and added dropwise to the mixture over 2 hours. After stirring at -70 ° C for an additional 1 hour, the temperature was gradually brought back to room temperature, followed by stirring for an additional 1 hour at room temperature. The reaction solution was poured into 150 ml of 50% aqueous hydrochloric acid, followed by stirring for 2 hours. After phase separation, the aqueous layer was extracted with 100 ml of ether. The organic layers were combined, washed with 30 ml of saturated sodium bicarbonate solution and then with 30 ml of saturated sodium chloride solution and dried over sodium sulfate. The ether was evaporated and the resulting residue was purified by chromatography on silica gel to obtain 5.1 g of the target compound (yield 26.6 g).

(5) 3- (3-thenyl) benzaldehyde.

A Grignard solution was obtained from 33.7 g of 3-bromobenzaldehyde diethyl acetal and 2.9 g of magnesium in 60 ml of tetrahydrofuran. Separately, a solution containing 13.3 g of 3-chloromethylthiophene, 1.0 g of copper (I) chloride and 30 ml of tetrahydrofuran was prepared and after displacement with nitrogen gas it was cooled to -10 ° C. The Grignard solution was added dropwise to this solution over 1.5 hours. After the addition was complete, the mixture was refluxed for 1 hour. After cooling to room temperature, the reaction solution was poured into 150 ml of ice water containing 10 g of ammonium chloride and then extracted with two 100 ml portions of ether. The ether layer was washed with 40 ml of water and dried over magnesium sulfate. After evaporation of the ether, the resulting residue was distilled in vacuo (bp 116-122 ° C / 0.2 mm Hg) to obtain 15.2 g of a colorless liquid (57.6% yield).

This product was 3- (3-thenyl) benzaldehyde diethyl acetal.

This acetal (10.0 g) was added to a 790 78 88 27 mixed solution containing 100 ml 5% aqueous hydrochloric acid, 30 ml toluene and 30 ml tetrahydrofuran, followed by stirring at 25 ° C for 15 hours. After phase separation, the aqueous layer was extracted with 100 ml of toluene. The organic layers were combined, washed with 30 ml of saturated sodium bicarbonate solution and then with 30 ml of saturated sodium chloride solution and dried over magnesium sulfate. The solvent was evaporated to obtain 6.8 g of a colorless liquid (yield 93.3%).

When applying the compounds of the invention as an insecticide or acaricide, they can be used as such without mixing with other ingredients, but generally they are used in the form of a pesticide composition by mixing with a carrier to improve its manageability as a pest control agent; and such a composition can be further diluted before use, if necessary.

In preparing pesticidal compositions, the compounds of the invention can be formulated in a manner consistent with the techniques used in conventional pesticides, which are well known to those skilled in the art, and no special precautions are required. The compounds according to the invention can be used for the intended application purpose in any of the forms such as emulsifiable concentrate, wettable powder, dusting powder, granules, fine granules, oil preparations, aerosol, heat-acting smoke-developing agent (mosquito coil, electric far heat mosquito mat), smoke-forming preparation that works without heating, poisonous bait, etc.

The compounds of the invention can be used in combinations of two or more members to enhance the insecticidal and acaricidal activity.

The activity can also be enhanced by mixing with synergists for pyretroids such as ol- (2- (2-butoxy-ethoxy) ethoxy) -4,5-methylenedioxy-2-propyloluene (referred to as piperonyl butoxide), 1-2 methylenedioxy-4- (2- 790 7 8 88, .28 (octylsulfinyl) propyl) benzene, 4.- (3,4-methylenedioxy-phenyl) -5-methyl-1,3-dioxane, N- (2 ethylhexyl) bicyclo [2,2,13 hepta-5-en-2,3-dicarboxyimide, octachlorodipropyl ether, isobornyl thiocyan acetate and other known synergists active for allethrin and pyrethrin.

While highly resistant to light, heat and oxidation, the compounds of the invention can be further stabilized against severe oxidative conditions by mixing with an appropriate amount of stabilizer. Suitable stabilizers are antioxidants and ultraviolet absorbers, including phenol derivatives and bisphenol derivatives such as BHT (2,6-di-tert-butyl-4-methylphenol) and BHA 15 (2-tert-butyl-4-methoxyphenol); arylamines such as phenylnaphthylamine, phenylnaphthylamine and phenetidine acetone condensate; and benzophenone compounds.

The compounds of the invention can be formulated to provide multi-purpose preparations having desired actions and, in some cases, even synergistic actions by mixing with various physiologically active substances including, for example, allethrin, N- (chrysanthemoxymethyl) ) -3,4,5,6-tetrahydrophthalimide, 5-benzyl-3-furylmethylchrysanthemate (referred to as "Chrysron"), 3-phenoxybenzylchrysanthemate, 5-propargyl-furylchrysanthemate, 2-methyl-5-propargyl-3-furylmethyl- chrysanthemum, d-trans, d-cis, trans-chrysanthemates thereof, pyrethrum extract, d-trans or d-cis, trans ester of d-alletrolone, other known cyclopropanecarboxylate esters; organophosphorus insecticides such as 0,0-dimethyl-0- (3-methyl-4-nitrophenyl) phosphorothioate (referred to as "Sumithion"), 0,0-dimethyl-0-4-cyanophenylphosphorothioate and 0,0-dimethyl-0- (2 2-dichlorovinyl) phosphate (referred to as dichlorvos); carbamate insecticides such as 1-naphthyl-N-methyl carbamate, 3,4-dimethylphenyl-N-methyl carbamate, m-tolyl-N-methyl carbamate, 0-sec.butylphenyl-N-methyl carbamate, 0-isopropoxyphenyl-N-methyl carbamate, 3- methyl 4-dimethylaminophenyl-N-monomethyl carbamate and 4-dimethyl-790 7 8 88 29% * * amino-3,5-xylylmethyl carbamate; other insecticides, fungicides, nematocides, acaricides, herbicides, plant growth regulators, fertilizers, microbial pesticides as described in ESRaun et al., J. Eco., 59_ (3), 5 620 (1966), insect hormones and other agricultural chemicals .

The insecticidal and / or acaricidal compositions according to the invention contain 0.001 to 80.0%, preferably 0.01 to 50% by weight, of an active ingredient.

Practical embodiments of the insecticidal or acaricidal compositions of the invention are illustrated in the following formulation examples, wherein parts and percentages are parts by weight and percentages by weight.

Formulation example 1.

10 parts of each of the compounds (1) to (43) of the invention were mixed with 15 parts of "Sorpol 3005X" (a mixture of a non-ionic surfactant, polyoxyethylene phenylphenol derivative, and an anionic surfactant substance, an alkyl aryl sulfate) and 75 parts of xylene. The mixture was carefully stirred, mixed and dissolved to give the respective 10% emulsifiable concentrates.

Formulation example 2.

0.3 parts of each of the compounds (1), (2), (3) and (4) according to the invention were dissolved in 20 parts of acetone, mixed with 99.7 parts of clay with a part-size of 48. Thoroughly stirred and freed from the acetone by evaporation to obtain 0.3% of powdered formulations of each compound. Formulation example 3.

50 parts of each of the compounds (1), (2), 35 (3), (4) and (6) of the invention were mixed well with 5 parts of "Sorpol 5029-0" (anionic surfactant, registered trademark of Toho Chemicals), mixed with 45 parts of diatomaceous earth having a particle size of 48 µm, and carefully mixed in a 79078 88 4, 30 mill to obtain a 50% wettable powder of each compound.

Formulation example 4.

10 parts of each of the compounds (1), (2), 5 (3), (4) and (6) of the invention were mixed with 5 parts of "fenitrothion", carefully mixed with 5 parts of "Sorpol 5029-0" , mixed with 80 parts of 48 pn diatomaceous earth and carefully mixed in a mill to obtain a 15% wettable powder of each compound. Formulation example 5.

To 2 parts of each of the compounds (1), (5), (6), (7), (26) and (41) according to the invention, 2 parts of sodium lignin sulfonate (a binder) were added, followed by addition of 96 parts of clay (cutting agent). The mixture was carefully mixed in a grinder, mixed with water in an amount of 10% of the resulting mixture, again carefully mixed, then granulated by a granulator and dried in an air stream to obtain 2% granules of each connection. Formulation example 6.

0.2 part of the compounds (1), (4), (5), (6),. (7) and X41) according to the invention were dissolved in lamp kerosene to a total of 100 parts to obtain a 0.2% oil spray.

Formulation example 7.

A mixture of 0.1 part of the compound (5) of the invention and 0.5 part of piperonyl butoxide 30 was dissolved in purified kerosene to a total of 100 parts to obtain a 0.1% oil spray. Formulation example 8.

A mixture of 0.1 part of the compound (6) of the invention and 0.2 part of "D.ichlorvos" was dissolved in purified kerosene to a total of 100 parts to obtain a 0.3% oil spray. Formulation example 9.

0.1 part of each of the compounds (5) and (6) according to the invention, 0.2 part "Resmethrin" ((1-cyclohexene-1,2-dicarboximido) methyl dl, cis, trans- 790 7 8 88 31 Chrysanthemate), 7 parts of xylene and 7.7 parts of deodorized kerosene were mixed to form a solution. An aerosol container was filled with the above solution and provided with a valve member 5 through which 85 parts of a propellant (LPG) was filled under pressure into the container to obtain an aerosol formulation containing 0.3% active ingredient. Formulation example 10.

0.4 parts of the compound (12) of the invention, 0.1 parts of "fenitrothion", 7 parts of xylene and 7.1 parts of deodorized kerosene were mixed to form a solution. In the same manner as in Formulation Example 9, an aerosol formulation containing 0.9% active ingredient was obtained from the above solution.

Formulation example 11.

0.4 parts of the compound (26) of the invention, 2.0 parts of piperonyl butoxide, 6.2 parts of xylene and 7 parts of deodorized kerosene were mixed to form a solution. An aerosol preparation containing 0.4% active ingredient was obtained in the same manner as in Formulation Example 9. Formulation Example 12.

0.5 g of PHT was added to 0.5 g of the present compound (19) and the mixture was dissolved in 20 ml of methanol. The solution was mixed homogeneously with stirring with 99.0 g of a mosquito coil carrier containing Tabu powder, pyrethrum marrow and wood powder in a ratio of 3: 5: 1, then the methanol was evaporated. 150 ml of water were added to the residue and the mixture was kneaded well, formed into a mosquito coil and dried. In this way, the mosquito coil of the present compound was obtained. Formulation example 13.

To 0.1 g of each of the present compounds (6) and (17), 0.2 g of the d-trans chrysanthemum ester of allethrin was added and the mixture was dissolved in 20 ml of methanol. The solution was mixed homogeneously with 99.65 g of a mosquito coil carrier 790 78 88 ... . 32 (described above) with stirring and then the methanol was evaporated. 150 ml of water were added to the residue and the mixture was kneaded well, formed into a mosquito coil and dried. In this way, the mosquito coil of each of the two compounds was obtained.

Formula example 14.

To 0.1 g of each of the present compounds. (5), (6) and (7) 0.1 g of BHT and 0.1 g of piperoyl butoxide were added and the mixture was dissolved in an appropriate amount of chloroform. The solution was adsorbed homogeneously in a 3.5 cm x 1.5 cm x 0.3 cm (thickness) filter paper. In this way, a fibrous smoke developer for heating on a hot plate 15 was obtained. As the fibrous support, products can be used which have the same effect as a tulip plate (filter paper), for example asbestos. Formulation example 15.

To 0.02 g of each of the present compounds (5), (6), (7) and (13) were added 0.05 g of 5-propargyl furfuryl dl-cis, trans-chrysanthemate and 0.1 g BHT added and the mixture was dissolved in an appropriate amount of chloroform. The solution was then adsorbed homogeneously in a 3.5 cm x 25 cm 1.5 cm x 0.3 cm filter paper. In this way, a fibrous smoke expeller for heating on a hot plate was obtained.

The exceptional insecticidal and acaricidal activity of compounds according to the invention is explained below with reference to test examples.

In these test examples, comparative preparations were prepared in the same manner as the test preparations using the known compounds listed in Table B.

Table B.

790 78 88 33 TABLE B.

No. Formula Literature (A) Formula 64 British Patent 1,413,491 5 (B) Formula 65 British Patent 1,413,491 (C) Formula 66 British Patent 1,413,491 (D) Formula 67 British Patent 10 1,413,491 (E) Pyretrine FBLaForge et al., J. Am. Chem.

Soc. 58, p. 1777 (1936).

(F) formula 68 T. Iwata c. s., J. Econ.

Entomol. 65 (3), p.

15, 643 (1972).

(G). formula 69 F. Munger et al., J. Econ.

Entomol. S3, (3), 384, (1960).

Trial example 1.

The present compounds (1), (4), (5), (6), (7), (8), (12), (13), (20), (25), (29), (30 ), (33), (37), (41) and (43) and the comparator were each formulated into oil sprays of four or five different concentrations using deodorized kerosene.

5 ml of the oil spray was sprayed by Campbel's turntable method (Soap and Sanitary Chemicals, JL4, No. 6, p. 119 (1938)). 20 sec. after spraying, the valve was opened and about 30 100 adult houseflies (Musea domestica) per group 790 78 88 34 were exposed to the descending mist for 10 min. Then the adults were transferred to a wire cage and left there at 26 ° C . After 24 hours, the mean lethal concentration (LC5q in mg / 100 5 ml) was calculated and the mortality at each concentration (average of 3 series of tests)? the results are shown in Table C.

TABLE C.

Test compound LC ™ after hours 10 (mg / 100 ml) 1 35 4 24 5 12 6 15 15/7 8 8 60 12 51 13 27 20 9 20 25 25 29 73 30 36 33 30 37 77 25 41 29 43 69 E 280

Trial example 2.

The present compounds (3), (4) and (5) 30 were each diluted to four or five different concentrations with acetone. A 12 cm diameter circle was drawn on aluminum foil and 1 ml of the above dilute acetone solution was placed inside the circle. After the acetone had evaporated, 35 adult males of German cockroaches (Blattella 7907 8 88 35 r * germanica) were released and covered with a 12 cm diameter polyethylene cup. After 48 hours, the mean lethal dose (LD ^ q in mg / m) was calculated from the mortality at each concentration (average of 5 three test series); the results are as shown in Table D.

TABLE D.

2

Test compound LD50 (m9 / m) 3 0.6 10 4 0.8 5 0.4 (A) 2.0 (B)> 5.0 (C)> 5.0 15 (D) -> 5.0

Test example 3.

Each of the emulsifiable concentrates described in Formulation Example 1 containing the present compounds (3), (4), (5), (6), (7), (12), 20 (13), (14), (20 ), (21), (25), (26), (29), and (33 L was diluted with water to an active ingredient content of 1 ppm. 100 ml of each emulsion was placed in a 180 ml plastic cup content and 30 larvae in the third stage of the yellow fever mosquito (Aedes 25 aegypti) were released into each cup After 24 hours, 100% mortality was observed in each cup (average of three test series).

Test example 4.

Each of the emulsifiable concentrates described in Formulation Example 1 containing the present compounds (1) to (43) was diluted with water to an active ingredient content of 500 ppm.

Butter was applied to the entire inner wall of a polyethylene cup (5.5 cm diameter) and a piece of 790 78 88 36 same size filter paper was placed on the bottom of the cup. 0.5 ml of each diluted solution was dropped onto the filter paper and 20 larvae 10 days after incubation of the German cockroach (Blattella germanica) were released into the cup which was then covered with a lid. After 24 hours, the dead and living animals were counted in order to obtain the mortality as an average of three test series; the results are shown in Table E.

TABLE E.

10 --------

Test compound Mortality Test compound Mortality after 24 hours after 24 hours (%) (%) 15 1 100 23 .90 2 100 24 100 3 100 25 100 4 100 26 100 5 100 27 100 20 6 100 28 90 7 100 29 100 8 100 30 100 9 100 31 100 10 100 32 100 25 11 100 33 100 12 100 34 100 13 100 35 100 14 100 36 95 15 95 37 100 30 16 85 38 95 17 85 39 90 18 80 40 100 £ 9 «100 41 100 20 100 42 100 35 21 100 43 9 5 22 100 Not treated 0 790 7 8 88 37

Sample 5,

The insecticidal activity on adult house flies (Musea domestics) of each aerosol obtained in formulation examples 9, 10 and 11 was tested according to the aerosol test method (Soap and

Chemical Specialties, Blue Book, 1965) using a Peet Grady chamber with a volume of 6,128 m. As a result, with each aerosol, more than 80% of the flies could be anesthetized 15 min after spraying and 100% of the flies could be killed by the following day (average of three test series).

Test example 6.

About 50 adult Northern House Sparrow-15 ticks (Culex pipiens pallens) were released into a 70 x 70 x 70 cm glass chamber in which a battery powered small electric fan (wing diameter 13 cm) was placed.

0.1 g of each of the mosquito coils obtained in Formulation Examples 12 and 13 was lit at one end and placed in the center of the bottom of the chamber. Each mosquito coil allowed more than 90% of the adult animals to be anesthetized within 20 minutes and more than 80% of the adult animals killed after 24 hours (average of three series of trials).

Test example 7.

Each of the wettable powders containing the present compounds (1) to (4) and (6) described in Formulation Example 3 was diluted with water to an active ingredient content of 400 ppm. The diluted preparation was applied to rice plants grown in a cup of 180 ml content in an amount of 15 ml per 2 cups. After air drying, the plants were covered with a mesh cage and 15 adult females of the small brown plant beetle (Laodelphax striatellus) were released into the cage. After 24 hours, the dead and live animals were observed and an average mortality from three 790 7 8 88 38 repeated experiments was obtained; the results are shown in Table F.

TABLE F.

Test compound Mortality (%) 5 1 100 2 100 3 100 4 100 6 100 10 C 10

Not treated 0

Test example 8.

The emulsifiable concentrate containing the present compounds (1), (2), (3), (4), (5), (6), 15 (9, '- (9), (12), (14), (26), (29) or (33), described in Formulation Example 1, was diluted with water to an active ingredient content of 5 ppm Five rice seedlings, 10 days after sowing, were immersed in the preparation for 1 min and in air dried.

The treated seedlings and 10 larvae in the third stage of the rice stem border (Chilo suppressalis) were placed in a plastic cup with a diameter of 5 cqu. After 10 days, 100% mortality was observed in each case (average of three test series). 25 Sample test 9.

Each of the emulsifiable concentrates, containing the present compounds (1) to (9), (12, (14), (26), (29) and (33 \) described in Formulation Example 1, was diluted with water to an active content 30 ppm component Leaves of runner bean plants were immersed in the emulsion for 1 min, air dried and placed in a polyethylene cup 10 cm in diameter and 4.5 cm high, together with 10 larvae in the third stage of the tobacco-cutworm (Spodoptera litura) After 2 days, 100% kill 790 78 88 39 was observed in each case (average of three series of trials).

Test example 10.

Each of the dusting powder compositions described in Formulation Example 2 was applied at 3 kg / 10 are to rice plants grown in a 1/10000 are Wagner pot. The plant was covered with a mesh cage and 15 adult females of the green rice leaf beetle (Nephotettix cincticeps), resistant to 10 carbamate compounds, were released into the cage.

The pot was kept in a greenhouse and after 24 hours the dead and living animals were observed. Mortalities in mean values from three repeated tests for each compound were as shown in Table G.

TABLE G.

Test compound Mortality (%) 1 100 2 100 20 3 100 4 100 F 30

Not treated 0 25 Test example 11,

Each of the emulsifiable concentrates containing the present compounds (2), (6), (12) and (14) described in Formulation Example 1 "was diluted with water to an active ingredient content of 500 ppm. The emulsion (500 ml) was sprayed on a tangerine seedling, planted in a 9 cm pot and parasitized by citrus red mites (Panonychus citri), resistant to throats (comparative compound G) at any growth stage. After 10 days, the number of 35 adult females on the plant was counted and rated according to the following criteria: 79078 88 40 ++: 0-9 adult females are parasitic to one. plant.

+; 10-30 adult females are parasitic on one plant.

5 -: 31 or more adult females are parasitic on one plant.

The average results of three test series are shown in Table H.

TABLE H.

10 Test compound Rating 2 ++ 6 ++ 12 ++ 14 ++

15 B

C G

Not treated -

Test Example 12, 20 Each of the emulsifiable concentrates, containing the present compounds described in Formulation Example 1, was diluted with water to an active compound content of 100 ppm. Each of the two leaves of runner bean plants (Phaseolus vulgaris) at the first leaf stage was cut into a 3 cm diameter circle. Each was dipped in test solutions for 1 min. After adhesive was applied to the stem, about 30 adult carmine mites (Tetranychus cinnabarinus) were released onto a treated leaf. After 48 hours, the number of mites on both leaves was counted. "Chasing Percentage" for a test compound was calculated from the following equation: 790 7 8 88 41

Backside percentage = ---- ïïËi-

Nal + - Na2 Nbl + Nb2 10Q

1. Nbl

Nbl + Nb2 5 In this equation means

Nal: number of mites on the untreated leaf of the test group?

Na2: number of mites on the treated leaf of the test group; 10 Nbl: number of mites on the untreated leaf of the control groups;

Nb2: number of mites on the treated leaf of the control groups.

The results, obtained as an average of three test series, are shown in Table J.

TABLE J.

Test compound Remaining mites (%) 6 95 9 80 20 12 90 G 5

Test example 13. (remaining operating test l

The emulsifiable concentrate containing the present compounds (2) and (4) described in Formulation Example 1 is diluted with water to an active ingredient content of 400 ppm. Rice plants grown in a Wagner pot were sprayed with 200 ml of the emulsion. After air drying, the plant was covered with a mesh cage and 15 adult females of the green rice leaf beetle (Nephotettix cincticeps) were released into the cage. Mortality after 24 hours was determined. In order to test the residual activity, the pot with grown rice plant was treated in the same manner as described above. 42 and left it for 7 days. In the same manner as described above, the test insects were released and mortality was determined after 24 hours. The above tests were performed in a greenhouse and the results obtained as an average of three test series are as shown in Table K.

TABLE K.

Test connection ___ Mortality (%) _

Immediately after 7 days after 10 treatment treatment 2 100 100 4 100 100 F 70 0

Not treated 0 0 15 Test example 14. (Test to determine mammalian toxicity)

Male mice (18-22 g) were administered each of the corn oil solutions of the present compounds (1), {2) ,, (3) and (29) orally, the dose being 0.2 ml / 10 g body weight amount. The 24-hour morality was observed and the mean lethal dose (LD ^ q in mg / kg) was calculated as an average from three test series; the results are as shown in Table L.

25 TABLE L.

Test compound LD50 (mg / kg) 1> 800 2> 800 3> 800 30 29> 800 A 650 E 370 F 60 79078 88 Conclusions.

Claims (4)

1. Cyclopropane carboxylates of the formula 1 of the formula sheet, wherein ^ and R2, which may be the same or different, each have a hydrogen or halogen atom or a methyl group, A an oxygen or a sulfur atom or a methylene group, R an oxygen atom or a group of the formula -CH = CH- and R 4 represent a hydrogen atom or an ethynyl or cyano group, and (a) R 9 represents a group of the formula 2 or 3 of 10, wherein R 1. a halogen atom, when A is an oxygen or sulfur atom and R is a group of the formula -CH = CH-, when A is a methylene group, R is a group of the formula -CH = CH- and R4 is a hydrogen atom, or when A a methylene-15 group, R is an oxygen atom and R ^ is a hydrogen atom or an ethynyl group, or (b) when A is a methylene group, R is a group of the formula -CH = CH- and R ^ is an ethynyl group, Rg is a group with represents formula 4 of formula sheet 20, wherein Rg is a hydrogen atom or a methyl group, where, when Rg is a hydrogen atom, Ry is a group of the formula 5 or 6 of the formula sheet (wherein Rg is a halogen atom or a methyl or methoxycarbonyl group and Rg represents a halogen atom or a methyl group) and when Rg is a methyl group, Ry is a methyl group, or (c) when A is a methylene group and R4 is a cyano group, Rg represents a group of the formula 7 in which R ^ is a hydrogen atom or a methyl group, where when, when R ^ q is a hydrogen atom, R ^ is a group of formula 8 or 6 of the formula sheet (wherein R12 is a halogen atom or a methyl, methoxycarbonyl or methoxymethyl group and R ^ g is a hydrogen or halogen atom or a methyl group) and when R ^ is a methyl group, R ^ is a methyl group. 79078 88, 44 A compound according to claim 1, characterized in that and R 2 are both a hydrogen atom, R a group of the formula -CH = CH-, R ^ a cyano group and R ^ a group of the formula 2, wherein R ^ 5 has the same meaning as defined in claim 1. 3. A compound according to claim 1, characterized in that R ^ and R2 are both a hydrogen atom, A is a methylene group, R is a group of the formula -CH = CH-, R ^ is a cyano group and R ^ is a group of the formula 7 of the formula sheet, wherein R ^ q and R. ^ are both a methyl group. 4. Λ-Cyano-3- (2-thienyloxy) benzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylate. 5. X-Cyano-3- (3-thienyloxy) benzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylate. 6. <X-Cyano-3- (2-thenyl) benzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylate. 7. Oi-Cyano-3- (3-thenyl) benzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylate. 8. Ot-Cyano-3- (3-thienyloxy) benzyl 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylate. 9. <X-Cyano-3- (2-thienyloxy) benzyl 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylate. 10. A process for preparing a compound according to claim 1, characterized in that (a) an alcohol of the formula 13 of the formula sheet, wherein R 1, R 2, A, R and R 4 have the same meanings as defined in claim 1, reacting with a carboxylic acid halide of formula 12 of the formula sheet, wherein R 1 has the same meaning as defined in claim 1 and Y is a halogen atom 79078 88, in an inert solvent in the presence of an organic tertiary base, or (b an alcohol of the formula 13 wherein R 2, R 2 # A, R and R 2 have the same meanings as defined in claim 1 reacts with an anhydride of a carboxylic acid of formula 10 of the formula sheet wherein R ^ has the same meaning as defined in claim 1, in an inert solvent, or (c) an alcohol of formula 13 wherein R ^, R2, A, R and R ^ has the same meanings as defined in claim 1 react with a carboxylic acid of the formula 10, wherein R 3 has the same meaning as defined in claim 1, in an inert solvent in the presence of a dehydrating agent or a condensing agent, or (d) a halide of the formula 9 of the formula sheet, wherein R 1, R 2, A , R and R ^ have the same meanings as defined in claims 1 and 20 X is a halogen, reacts with a carboxylic acid of the formula 10, wherein R ^ has the same meaning as defined in claim 1, in an inert solvent in the presence of an organic tertiary base, or 25 (e) a halide of the formula 9, wherein R 1, R 2, A, R and R 1 have the same meanings as defined in claim 1 and X is a halogen, reacts with an alkali metal salt of a carboxylic acid of formula 10, wherein R 3 has the same meaning as defined in claim 1, in the presence of a phase transfer catalyst in a 2-phase system consisting of water and an inert solvent with little solubility r is in water. 11. A process for the preparation of a compound according to claim 1, wherein R 1 represents a cyano group, characterized in that (a) an aldehyde of the formula II of the formula sheet, wherein R 1, R 2, A and R have the same meanings as defined in claim 1, reacts * 7 ft ft * 7 ® OO ι »with a carboxylic acid halide of the formula 12 wherein has the same meaning as defined in claim 1 and Y is a halogen atom, and an alkali language cyanide in an inert solvent in the presence of a phase transfer catalyst, or (¾ an aldehyde of the formula 11, wherein, R 2, A and R have the same meanings as defined in claim 1, react with a carboxylic acid halide of the formula 12, wherein R 1 has the same meaning has as defined in claim 1 and Y is a halogen atom, and an alkali metal cyanide in the presence of a phase transfer catalyst in a 2-phase system consisting of water and an inert solvent with little solubility is in water. An aldehyde of the formula 11, wherein R 1 # r 2, A and r have the same meanings as defined in claim 1. Aldehyde according to claim 12, characterized in that R 1 and R 2 both represent a hydrogen atom, an oxygen or sulfur atom and R a group of the formula -CH = CH-. Aldehyde according to claim 12, characterized in that R 1 and R 2 both represent a hydrogen atom, A a methylene group and R a group of the formula -CH = CH-. 15. Aldehyde according to claim 12, characterized in that R 1 and R 2 both represent a hydrogen atom, A a methylene group and R an oxygen atom. 16. A process for preparing an aldehyde according to claim 12, characterized in that an alcohol of formula 15 of the formula sheet, wherein R 1, R 2, A and R have the same meanings as defined in claim 1, is reacted with an oxidizing agent in an inert solvent. Process for preparing an aldehyde 79078 88 according to claim 13, characterized in that a thiophene halide of the formula 19, wherein R 1 has the same meaning as defined in claim 1 and E is a halogen atom, is reacted with an alkali metal salt of the aldehyde of the formula 20 of the formula sheet, wherein 1 * 2 and A have the same meanings as defined in claim 1, or an alkali metal salt of its acetal in an inert solvent and when the acetal 10 is used, the resulting acetal returns to the aldehyde. 18. Process for the preparation of an aldehyde according to claim 12, characterized in that a metal salt of thiophene of the formula 21 of the formula sheet is used, in which the same meaning as defined in claim 1 and G is an alkali metal or a group with the formula MgJ, wherein J is a halogen atom, reacts with an acetal of the aldehyde of the formula 22 of the formula sheet, wherein and R have the same meanings as defined in claim 1 and L is a halogen atom, in an inert solvent and then returns the resulting acetal to the aldehyde. 19. A process for the preparation of an aldehyde according to claim 12, characterized in that a halomethyl derivative of thiophene of the formula 23 of the formula sheet, wherein R 1 has the same meaning as defined in claim 1 and Q is a halogen atom. reacting with an acetal of the haloaldehyde Grignard reagent of the formula 24, wherein R and R 2 have the same meanings as defined in claim 1 and J is a halogen, in an inert solvent and then returns the resulting acetal to the aldehyde. 20. Insecticidal and / or acaricidal composition, characterized in that this active ingredient is an insecticidal and / or acaricidal effective 79078 88. * * amount of a compound according to any one of claims 1-9, together with an inert carrier. 21. Method for controlling insects and / or acarides, characterized in that an insecticidally and / or acaricidally effective amount of a compound according to any one of claims 1-9 is applied to the insects, mites and / or ticks. 790 78 88 R? Rh R, - [j- -f-CHOC - R_ 1 TJJ ii 3 S o -CH - CH - CH = C 3 V Vr5 / \ 2 CH3 ch ^ 1 4 -CH - CH - CH = N - OCH., \ / 3 C Λ / \ 3 ch3 ch3 Sumitomo Chemical Company, Limited 790 78 88 II * *, -CH - * \ / \ 4 Nc R7 / \ CH3 CH3 -CH = S 5 Xr9 4 -CH = N - OCH » 3. Sumitomo Chemical Company, Limited 790 7 8 88 111 -CH-10 \ / R11 7 / \ ch3 ch3 / R, -CH = Ld 8 \ d K13 * ι> Λ Rl —- A-Of CHX 9 SR 7907 8 88 Sumitomo Chemcical Company, Limited IV R, - C - OH 10 J II o R2 _ r R1 - [- 4-A- [f- Ij-CHO 11 i R, - C - Y 12 3. ii o Sumitomo Chemical Company, Limited 79078 88 V R2 jS Ri — t [“II— A — PI CH - 0H 13 VV -Z> Ri ^ ~ ^ A ~ tl ~~ CH 1 SRR, 2 15 r1-4 J- a-T + J-ch2oh 5 Sumitomo Chemical Company, Limited 790 7 8 88 η, VI (ϊΰ) I 2 ΠΊ <νη-0 * '- 0 CH2OH 17 o-ch2-Ó s! CH2OH Och2-^ ^ S ^ 0 # # Sumitomo Chemical Company, Limited 790 7 8 88 VII RlHjf ~ 3 ~ E 19 S HYyCH0 20 R2 * i · ι-φ- »Sumitomo Chemical Company, Limited 790 78 88 VIII R2, yCHQ L— CH? - (ff V 22 * 1-ζ? 23 tf fi2!, CHO 24 Sumitomo Chemical Company, Limited 79078 88 IX *, / Cl CH - QC-CH - CH-CH = C ^ o- <5 11 XS CH3 CH3 25 / Cl CH - 0-C-CH - CH-CH = C ^ / r ^ C II xca 26 -------- \ „3 s # f = CH / Cl 27 .CH -OC-CH - CH-CH = C ^ 0-0 1 x S '= / CH3 CH3 Sumitomo Chemical Company, Limited 79078 88 X c = CH I / Cl CH-OC-CH - CH-CH = C' f \ II \ y xct / Cl CH-OC-CH - CH-CH = C ^ Oc / 50) <S CH 3 CH 3 * N X 1 CH-OC-CH - CH-CH = CC; 30 II V / ry ° -0 ° ch3 Xch3 / 3 / Sumitomo Chemical Company, Limited 790 78 88 xi / Cl CH 2 -QC-CH - CH-CH = C / 2 µl / Nil Q - ^ - O ° chJ Xch3 / Ci CHp-QC-CH - CH-CH = C ^ vV "___________ * C Ξ CH I JCl CH-OC-CH - CH-CH = C; 0-» r0 * XS CH3 CH3 Sumitomo Chemical Company, Limited 79078 88 XII C Ξ CH I xi CH-OC-CH - CH-CH = CV r <'IV ct (JCH ^ 0 «ζ \ h3 XI CH-OC-CH - CH-CH = C ^ 0 -« "rÖ ! X 3 CH3 CH3 * CN I / CL CH-OC-CH - CH-CII = C ^ ζτζ II V Xci (JCHr0_ ° «ί Xch3 Sumitomo Chemical Company, Limited 790 78 88 XIII C Ξ CH) / CH CH-OC-CH - CH-CH = C '-5 0- «r0! X C "J S <CH-j CH- 3 3 37 C = CH I / CH. CH-O-C-CH - C (5 0-« 2 {t i x ch3 _________________________? L_ 3. W CH3 CH3 t CN 1 / CH3 39 XH-OC-CH-X -5 II / N) H (yes * -0 '' ο », Sumitomo Chemical Company, Limited 79078 88., Xiv C = CH [ CQQCH CH-OC-CH - CH-CH = C ^ -3 II XCH 40 nr-cH2-f> 0 / \ cy ch3 ch3 CN I yF, CH-OC-CH - CH-CH = C ^ 41 / X 11 VF r ^ CH2 ~ \ _7 0 / \ ^ y 2 CH ^ CH ^ t CN I> Br CH-OC-CH - CH-CH = C 42 r <11 V Br (J ° ^ ° cl * 3 ^ ch3 Sumitomo Chemical Company, Limited 79078 88 XV ™ / Br CHOC-CH - CH-CH = C ^ 0 - Ö X CHj CH ^ 43 CM „_„ CH-OC-CH - CH-CH = N-0- CHo. 0- ^ 3 ί x ώ N == / CH3 CH3 -------------- CN 1 CH -O-CH- CH-OC-CH - CH-CH = C; * 3 Ο-ο, -Ö X “> S * N = / ch3 ch3 Sumitomo Chemical Company, Limited 79078 88 *» XVI J »C = CH I / Ci. CH-OC-CH - CH-CH = X 0-3 -0 'XW CH3 CH3 46 CN I / Cl ÖCH-GC-CH - CH-CH = CT ii \ χ xci ΛΊ 0 / \ ^ CH3 CH3 «4 CN I Cl CH-OC-CH - CH-CH = C' Br_O-0-Ö o X x “ 5 N = / CH3 CH3 Sumitomo Chemical Company, Limited 79078 88 XVII # t «OH I / Cl '·>. CHOC-CH - CH-CII = CX / T \ / r (AV“ 49 c 9.-II yo / \ xs N == / ch3 ch3 c: i 1 / CII3 .CH-OC-CH - (TJ 5 X! 3. CH3 CH3 i f \ ,: v - CII-CII = C ^ 21! \ / 0 / \ Cii3 cu3 o umitomo Chemical Company 79078 88-XVIII y-CH. -OC-CH-CH-CII = CV 0. X Xcz 0, 3 ™ 3 52 l yen A Y-CH-CC-CII - 011-011 = 0 ^ „s 2 X) II X / Nu 53 0 Λ CH3 CIi3 f Λ ΓΛ fr '. CA 54 / / ~ T ~ C! L'- '\ X — Cir-OC-CH - C! I —Cli = cX h V *' 0 II \ - / ^ CA N ':' 'C _C! IJ “lo Sumitomo Chemical Company, Limited 790 78 88 * XIX C = C [[aCI [2-O-CH-OC-CII-CH-CH = C / C.,. II O II / xcs, 55 o / \ CII3 CH3 XSL / 7-n / n -CHn-OC-CH-cn-CH = c; 0 -, - 0 ii vc £ V "0 0 / \ 56 ____ CH3 _ ™ 3» t r -;> JIIIQ £ / T ~ ÏÏ CH-OC-CI! - CH-CII = C ^ If 'Γ' VM] | VM · "'CIU CIL 3 y / l Sumitomo Chemical Company, Limited i 79078 88 *, * XX ^ C -cl {'? yCi ο “(IV — CHo-0C-CH - CH-CII = C ^ ο '2 II \ / \ C £ o / \ 58 CH3 ch ^ yCZ / 7-n-CHp-OC — CH - CII-CI! = C fl 2 V 0 / Cx 59 CH, CH, - JJ - ί ^ VC !!., - ^^ - ^!., - GC-CH - Cli-CINC ^ - “0 h || \ / \ F 60 0 Λ Cil3 CII V7- Sumitomo Chemical Company, Limited J 790 7 8 88 XXI /1—η—CHnCH.-OC-CH - CH — CH = CO 0 li V XBr S = o / cx CH3 CH ^ 61 CN Q -CX2-O-ch-oc-ch - c / CH3 ,, s 0 II \ / XCH, 62 o / \ 3 CH3__CH3 4 CHj - ^ VcH.-OC-CH - CH-CH = N-0-CH, S 0 II / 3 0 / C \ CH3 CH3 Sumitomo Chemical Company, Limited 79078 88 * u XXII CHrt-OC -CH - CH ri O-tf s? «2-OL 65 I 0 ^ CH.-OC-CK - CH ro c ^ ch 2 || \ / \ ch = c / C £ o / \ CH c \ r, CH3 CH3 t € / ^ NrCO · ^ 66 N-CH.j-0-C-CH - CH Cl ^ Aco · '2 II y \ CH = c (CH3 \ h3 cl Sumitomo Chemical Company, Limited 790 7 8 88 XXIII * -1 v CN 0 0 / \ \ c £ ch3 ch3 68 / CH3 CH ^ NHCOO ~ ^ ry ~ CH3 <OH cctj Sumitomo Chemical Company, Limited 790 78 88