NL8004278A - NEW CARBONIC ACID ESTER, METHOD FOR PREPARING THE SAME, AND INSECTICIDE COMPOSITION BASED ON THAT. - Google Patents

Description

S '- 1 -

Novel carboxylic acid ester, process for its preparation, and insecticide composition based thereon.

The invention relates to new carboxylic acid esters of the formula I of the formula sheet, wherein X is a chlorine, bromine or fluorine atom, as well as to the preparation thereof, and insecticides of low toxicity and fast action, containing this ester of active ingredient .

Since many infectious diseases are caused by insects, eradication of these insects is very effective in preventing the spread of these diseases, and the use of insecticides is the most effective means of achieving this goal. Consequently, the role of insecticides in maintaining a high standard of living for the human race is of great importance. Many superior insecticides have so far been invented to achieve this goal and have been used in various areas with good results.

However, organic chlorine insecticides such as BHC and DDT and organic phosphorus insecticides are severely limited in their use because they cause insects to become resistant to these agents and cause various problems such as environmental contamination and toxicity to organisms to which the target is is not targeted. Also with new insecticides, which have been substituted for the above, this problem of resistant insects has now become serious in different areas. Under these conditions, the development of new and even superior insecticides is highly desirable. Properties essential for insecticides are the following: a high insecticidal activity and knockdown effect are of course necessary, but in addition there is currently a low toxicity to unintended organisms, such as mammals, the lack of persistence, and highly requires low pollution of the environment.

Natural pyrethrin is low in mammalian toxicity 800 4 2 78 - 2 - and easily decomposable in open-air conditions, so that it has some of the above properties essential for insecticides. However, its insecticidal activity is relatively low compared to the organic phosphates and carbamates, and in addition it decomposes too quickly to give a residual effect, and is expensive. See "Advantages and Disadvantages of Pyrethrum" in "Pyrethrum" (JE Casida, Academy Press, New York and London, 1973) pp. 307-311].

The inventors have extensively studied the development of compounds that overcome the drawbacks of natural pyrethrin and are superior to insecticides currently in use. As a result, it has been found that the compounds of formula III have the following properties: 1) Remarkably fast effect (knockdown effect) and high insecticidal activity; 2) Relatively low toxicity to mammals; 3) Excellent insecticidal activity against insects, which are resistant to organic phosphates and carbamates; 4) Can be produced at a relatively low cost.

Based on this research, the present invention was developed.

The compounds of the invention are broadly encompassed within the framework of published Unexamined Japanese Patent Application 47531/1974. However, in this patent application there is no specific description of the compounds, and nothing is mentioned about the physical properties, the synthetic examples, and the insecticidal activity of the compounds.

In accordance with the present invention, it was first found that the compounds of formula 1 have a markedly higher knockdown effect than any compound in said Japanese patent application. Consequently, the invention has great significance.

The compounds of the invention can be obtained by reacting a carboxylic acid of formula 2 of the formula sheet, wherein X is defined as above, or a 40. reactive derivative thereof, with an alcohol 800 42 78 ν 4 - 3 - or a reactive derivative thereof of the formula 3 of the formula sheet, wherein A is a hydroxyl group or a tosyloxy group, in the presence of a suitable solvent, reaction aid and catalyst if necessary.

The reactive derivative of the carboxylic acid of formula 2 includes, for example, acid halides, acid anhydrides, lower alkyl esters, alkali metal salts and organic tertiary base salts. The reactive derivative of the alcohol of formula 3 includes, for example, compounds obtained by replacing the hydroxyl group of the alcohol with a halogen atom or a tosyloxy group.

The carboxylic acid esters of formula 1 have isomeric forms, ie geometric isomers (cis and trans isomers) based on the steric configuration of the carboxylic acid unit, and optical isomers based on the asymmetric carbon atoms of the carboxylic acid and alcohol units. All these isomers are of course also included within the scope of the invention.

Briefly, the process for preparing the carboxylic acid esters of the invention is that the carboxylic acid ester of formula 1 is prepared by reacting a carboxylic acid of formula 2, wherein X is as defined above, or a reactive derivative thereof, with an alcohol or a reactive derivative thereof of the formula 3, wherein A is a hydroxyl group or a tosyloxy group. The above reactive derivative of the carboxylic acid is further an acid halide (acid chloride or acid bromide) or acid anhydride, when A in formula 3 is a hydroxyl group, and is an alkali metal salt of the acid when A in formula 3 is a tosyloxy group. This means:

Synthesis A: reaction between alcohol and carboxylic acid halide.

The intended ester of formula 1 is obtained by reacting an alcohol of formula 3 'of the formula sheet with a carboxylic acid halide (chloride or bromide), preferably carboxylic acid chloride of formula 2, wherein X is as defined above, at -30 to 100 ° C for 0.5 to 20 hours in an inert solvent (e.g.

40 benzene, toluene, hexane, ether) in the presence of an 8004278-4 base (e.g. pyridine, triethylamine).

The base is preferably used in an amount of 1.0 to 3.0 mol based on 1 mol of the alcohol of formula 31. Furthermore, the amount of the carboxylic acid halide of formula 2 used is 1.0 to 1.5 mol, based on 1 mole of the alcohol of formula 3 '.

Synthesis B: reaction between alcohol and carboxylic anhydride.

The intended ester of formula 1 is obtained by reacting an alcohol of formula 3 'with a carboxylic anhydride of formula 2, wherein X is as defined above, at -20 to 100 ° C for 1 to 20 hours in an inert solvent (eg benzene, toluene, hexane, acetone) in the presence of a base (eg pyridine, triethylamine).

The base is usually used in an amount of 1.0 to 3.0 moles based on 1 mole of the alcohol of formula 3 '. Furthermore, the amount of the carboxylic anhydride of formula 2 used is 1.0 to 1.5 moles based on 1 mole of the alcohol of formula 3 '.

Synthesis C: dehydration reaction between alcohol and carboxylic acid.

The intended ester of formula 1 is obtained by reacting an alcohol of formula 3 '25 with a carboxylic acid of formula 2, wherein X is as defined above, at 0 ° to 150 ° C for 0.5 to 10 hours in a inert solvent (e.g. benzene, toluene, ether, acetone) in the presence of a dehydrating agent (e.g. dicyclohexylcarbodiimide).

The desiccant is usually used in an amount of 1.0 to 2.0 moles based on 1 mole of the alcohol of formula 3 '. Furthermore, the amount of the carboxylic acid of formula 2 is 1.0 to 1.5 moles based on 1 mole of the alcohol of formula 31.

Synthesis D: reaction between alcohol tosylate and carboxylic acid salt.

The intended ester of formula 1 is obtained by reacting an alcohol tosylate of formula 3, wherein is is a tosyloxy group, with an alkali metal salt 40 of a carboxylic acid represented by formula 4 of the 800 42 78 * - 5 formula sheet, wherein X is as defined above, and M is a sodium or potassium atom, at 0 to 1509C for 0.5 to 10 hours in an inert solvent (e.g. benzene, toluene, acetone, dimethylformamide, dimethyl sulfoxide).

The amount of the alkali metal salt of carboxylic acid represented by formula 4 used is 1.0 to 1.5 mol based on 1 mol of the alcohol tosylate of formula 3.

The carboxylic acid ester of formula 1, obtained by the above methods, can be purified by chromatography or distillation, if necessary.

The invention will be elucidated below in detail by means of the following examples,

15 which are not intended to limit the invention thereto. EXAMPLE I

(+) - 2-Methyl-3-2'-propynylcyclopent-2-en-4-on-1-ol (3.0 g) and pyridine (2.4 g) were dissolved in toluene (50 ml), and (+) - 2,2-dimethyl-3-cis-2 ', 2'-dichlorovinyl-20 cyclopropanecarboxylic anhydride (8.0 g) was added, followed by stirring at 40 ° C for 24 hours. The reaction solution was poured into an aqueous hydrochloric acid solution and separated into aqueous and toluene layers. The toluene layer was washed with a 5% aqueous potassium carbonate solution and then with an aqueous sodium chloride solution, and the solvent was removed by evaporation to yield 6.6 g of the pale yellow oil. This oil was purified by silica gel chromatography (developing solvent, n-hexane / ethyl acetate mixture) to give 4.1 g (+) - 2-methyl-3-2, -propynylcyclopent-2-en-4-on-1 -yl (+) - 2,2-dimethyl-3-cis-21,2'-dichlorovinylcyclopropane carboxylate (compound A) was obtained.

Refractive index 1.5310 (22.5 ° C).

EXAMPLE II

35 (+) -2-Methyl-3-21-propynyl-cyclopent-2-en-4-on-1-ol-tosylate (3.0 g) was dissolved in dimethylformamide (50 ml) and potassium ( +) - 2,2-dimethyl-3-trans-2 ', 2'-dichlorovinylcyclopropanecarboxylate (2.5 g) was added, followed by stirring at 60 ° C for 15 hours. The reaction 40 solution was poured into an aqueous hydrochloric acid solution 800 42 78-6 in extracted with ethyl acetate. The ethyl acetate layer was washed with a 5% aqueous potassium carbonate solution and then with an aqueous sodium chloride solution, and the solvent was removed by evaporation to give 2.8 g of a pale yellow oil. This oil was purified by silica gel chromatography (development solvent n-hexane / ethyl acetate mixture) to yield 2.1 g (+) - 2-methyl-3-21-propynyl-cyclopent-2-en-4-on-1- yl (+) - 2,2-dimethyl-3-trans-2 ', 2'-dichlorovinylcyclopropane-10 carboxylate (compound B) was obtained.

Refractive index 1.5282 (22.5 ° C).

EXAMPLE III

(+) - 2-Methyl-3-2'-propynylcyclopent-2-en-4-on-1-ol (320 mg) and pyridine (240 mg) were dissolved in toluene 15 (10 ml), and (+) -2,2-dimethyl-3-trans-21,21-difluorovinyl-cyclopropanecarboxylic acid chloride (420 mg) was added dropwise, followed by stirring at room temperature for 5 hours. The reaction solution was poured into an aqueous hydrochloric acid solution and separated into aqueous and toluene layers. The toluene layer was washed with an aqueous sodium bicarbonate solution and then with an aqueous sodium chloride solution, and the solvent was removed by evaporation to give 680 mg of a light yellow oil. This oil was purified by silica gel chromatography (developing solvent n-hexane / ethyl acetate mixture) to yield 450 g (+) - 2-methyl-3-2'-propynylcyclopent-2-en-4-on-1-yl (+) -2,2-dimethyl-3-trans-2 ', 21-difluorovinylcyclopropene carboxylate (compound C) was obtained.

Refractive index 1.4921 (25.0 ° C).

EXAMPLE IV

(+) - 2-Methyl-3-2'-propynyl-cyclopent-2-en-4-on-1-ol (150 mg) was dissolved in toluene (10 ml), and (+) - 2.2- dimethyl-3-cis-2 ', 2'-dibromovinylcyclopropanecarboxylic acid 35 (300mg) and dicyclohexylcarbodiimide (400mg) were added, followed by stirring at room temperature for 5 hours. The reaction solution was poured into an aqueous hydrochloric acid solution and separated into aqueous and toluene layers. The toluene layer was washed with a 40 sodium bicarbonate aqueous solution and then with 800 4 2 78 * -1-7 an aqueous sodium chloride solution, and the solvent was removed by evaporation to give 410 mg of a pale yellow oil. This oil was purified by silica gel chromatography (developing solvent, n-hexane / ethyl acetate mixture) to give 320 mg (+) - 2-methyl-3-2'-propynylcyclopent-2-en-4-on-1-yl (+) - 2,2-dimethyl-3-cis-2 ', 2'-dibromo-vinylcyciopropanecarboxylate (compound D) was obtained.

Refractive index 1.5621 (22.5 °).

10 EXAMPLE V

(+) - 2-Methy1-3-21-propynycyclopent-2-en-4-on-1-o1 (150 mg) and pyridine (120 mg) were dissolved in toluene (10 ml), and (+) - 2 2,2-dimethyl-3-cis-2,2,2'-dichlorovinyl-cyclopropanecarboxylic acid chloride (220 mg) was added dropwise, followed by stirring at room temperature for 5 hours. The reaction solution was poured into a 5% aqueous hydrochloric acid solution and separated into aqueous and toluene layers. The toluene layer was washed with an aqueous sodium bicarbonate solution and then with an aqueous sodium chloride solution, and the solvent was removed by evaporation to give 320 mg of a pale yellow oil. This oil was purified by silica gel chromatography (developing solvent, n-hexane / ethyl acetate mixture) to give 270 mg (+) - 2-methyl-3-21-propynylcyclopent-2-en-4-on-1-yl ( +) - 2,2-dimethyl-3-cis-21,2'-dichlorovinylcyclopropane carboxylate (compound E) was obtained.

Refractive index 1.5298 (24.0 ° C).

EXAMPLE VI

30 (+) - 2-Methyl-3-21-propynyl-cyclopent-2-en-4-on-1-ol (1.50 g) and pyridine (1.20 g) were dissolved in toluene (30 ml) , and (+) - 2,2-dimethyl-3-cis, trans-2 ', 2'-dichloro-vinylcyclopropanecarboxylic acid chloride (2.28 g) was added dropwise, followed by stirring at 20 ° C for 5 hours. The reaction solution was poured into a 5% aqueous hydrochloric acid solution and separated into aqueous and toluene layers. The toluene layer was washed with an aqueous sodium bicarbonate solution and then with an aqueous sodium chloride solution, and dried over 40 magnesium sulfate. The solvent was removed by evaporation 8004278-8, and the residue purified by silica gel chromatography (developing solvent, n-hexane / ethyl acetate mixture) to yield 2.50 g (+) - 2-methyl-3-2'-propynyl cyclopentent -2-and-4-on-1-yl (+) - 2,2-dimethyl-3-cis, 5 trans-2 ', 2'-dichlorovinylcyclopropanecarboxylate (compound F) was obtained.

Refractive index 1.5290 (22.5 ° C).

The compounds of the formula I according to the invention have a very rapid action on harmful insects, such as flies, mosquitoes, and cockroaches, which are harmful to health, and in addition they are very useful for controlling insects that are harmful to agricultural crops, such as various species. grasshoppers, cutworms, the diamondback moth (Plutella xylostella), leaf rollers, 15 aphids, stem borers, as well as insects, harmful to stored cereals, such as the Indian meal moth (Plodia interpunctella) and rice beetles (Sitophilus zeamais) and animal parasitic lice and ticks. Furthermore, they are effective for controlling other harmful insects. The compounds of the invention furthermore have an effect not only on the knockdown of insects to kill them, but also an ability to repel, i.e., an activity to repel insects from their host plants.

The excellent properties of the carboxylic acid ester of formula 1 are most notable at (+) - 2-methyl-3-21-propynylcyclopent-2-en-4-on-1-yl (+) - 2,2- dimethyl-3-cis, trans-2 ', 21-dichlorovinylcyclopropane carboxylate, (+) - 2-methyl-3-2'-propynylcyclopent-2-en-4-on-30 1-yl - (+) - 2 , 2-dimethyl-3-trans-21,2'-difluorovinylcyclopropane carboxylate and (+) - 2-methyl-3-21-propynylcyclopent-2-en-4-on-1-yl (+) - 2,2 dimethyl-3-cis-2 ', 2'-dibromovinyl cyclopropane carboxylate.

The compounds of the invention can be practically used for these purposes in various preparation forms.

In order to make it clearer that the compounds of the invention have excellent properties, experimental examples are given below. The compounds of formula 1 other than 800 42 78 t-9 - than those described in the examples also have the same tendency.

Test Example 1 0.1 Part of each of the compounds and reference 5 compounds were dissolved in deodorized kerosene to a total weight of 100 parts together with kerosene to obtain an oil spray of each compound.

Ten female adult specimens of the Northern House Mosquito (Culex pipiens pallens) and ten adult specimens of the Housefly (Musea domestica) were released.

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left in a 70 cm glass chamber, and 0.7 ml of the above oil spray was sprayed into the chamber.

Thereafter, the number of insects deposited was counted with the passage of time, and the value of KT / g was obtained from the average precipitation ratio of three repeated experiments according to Finney's method. After 10 minutes, the test insects were collected and given a 5% aqueous sugar solution, and after 24 hours the dead and live specimens were counted.

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Trial example 2

A 0.1% oil spray agent of each of the compounds of the invention and the reference compound was prepared using deodorized kerosene 5 as the solvent.

Ten adult German cockroaches (Blattella germanica) were released into a 10 cm diameter glass Petri dish, the inner wall of which was thickly coated with petroleum jelly, and the dish was covered with a nylon mesh 10 of mesh size 50. Then 0.6 ml of the oil spray agent sprayed at a distance of 50 cm from the disk using a glass atomizer, and the number of insects deposited was counted after 5, 10 and 20 min.

15 TABLE B

precipitation ratio (%)

Test compound - after 5 min. After 10 min. After 20 min.

Compound A (invent.) 93 100 100 20 Compound B "90 100 100

Compound C "100 100 100

Compound D "97 100 100

Compound E "100 100 100

Compound F "90 100 100 25 Allethrin 0 30 60

In producing an insecticide and acaricide using the compounds of the invention (Formula 1), the compounds can be formulated in the same manner as the conventional pyrethroids in desired preparation forms using diluents for the conventional insecticides by methods known to those skilled in the art are well known. The preparation forms include, for example, oil sprays, emulsifiable concentrates, dust powders, aerosols, wettable powders, granules, mosquito wraps, fumigants, whether heated or not, powdered or solid bait containing attractants, 8004278-13 and other optional forms.

An increased insecticidal action can be further developed by mixing two or more of these compounds. Also, the insecticidal activity of the compounds of the invention can be increased by mixing them with pyrethroid synergists or other known effective synergists for allethrin and pyrethrin. The synergists of pyrethroids include, for example, α-2- 2- (2-butoxyethoxy) ethoxyl 4,5-methylene-dioxy-2-propyl-10 toluene (hereinafter referred to as piperonyl butoxide), 1,2-methylenedioxy-4- £ 2 - (octylsylfinyl) propyl [Jbenzene (hereinafter referred to as sulfoxide), 4- (3,4-methylenedioxyphenyl) - 5-methyl-1,3-dioxane (hereinafter referred to as sulfoxane), N- (2-ethylhexyl) bicyclo-2,2,11hepta-5-en-2,3-dicarboximide 15 (hereinafter referred to as MGK-264), octachlorodipropyl ether (hereinafter referred to as S-421) and isobornylthiocyanoacetate (hereinafter) to be designated as Thanite).

Generally, carboxylic acid esters tend to have poor resistance to light, heat and oxidation, and therefore compositions of more stable effect can be obtained by adding an appropriate amount of stabilizers. These stabilizers include, for example, antioxidants and ultraviolet absorbers such as phenol derivatives (eg BHT, BHA), bisphenol derivatives, arylamines (eg phenyl-α-naphthylamine, phenyl-g-naphthylamine, condensation products of phenetidine and acetone), and benzophenone compounds.

Furthermore, multi-purpose compositions of excellent efficacy can be produced by mixing with other active ingredients, eg, allethrin, N- (chrysanthemoxymethyl) -3,4,5,6-tetrahydrofthalimide (hereinafter referred to as tetramethrin), 5- benzyl-3-furylmethylchrysanthemate (hereinafter referred to as resmethrine), 3-phenoxybenzylchrysanthemate (hereinafter referred to as phenothrine), 5-proppargylfurfurylchrysanthemate, 2-methyl-5-propargyl-3-furylmethylchrysanthemate, d-trans or d-cis trans isomers of these chrysanthemates, pyrethrum extracts, d-trans or d-cis.trans-chrysanthemum esters of d-allethrolone; 3-phenoxybenzyl-2,2-dimethyl-3- (2,2-40 dichlorovinyl) cyclopropanecarboxylate, α-cyano-3-phenoxy-800 4 2 78 - ± * ± benzyl-2 ', 2'-dimethyl-31 - (2,2-dichlorovinyl) -cyclopropane carboxylate, α-cyano-3-phenoxybenzyl 2 ^ 2 ^ 3 ^ 31-tetra-methylcyclopropane carboxylate, α-cyano-3-phenoxybenzyl 2- (4-chlorophenyl) isovalerate and other known cyclopropane -5 carboxylic acid esters; organic phosphorus insecticides such as 0,0-dimethyl 0- (3-methyl-4-nitrophenyl) phosphorothioate (hereinafter referred to as phenitrothion), 0,0-dimethyl 0-4-cyano-phenylphosphorothioate (hereinafter referred to as Cyanophos), 0,0-dimethyl 0- (2,2-dichlorovinyl) phosphate (hereinafter referred to as Dichlorvos), Baycid, Vinyphate, Malathion, Salithion, Papthion, Dipterex and Diazinon; carbamate insecticides such as 1-naphthylN-methyl carbamate, 3,4-dimethylphenyl N-methyl carbamate, 3-methylphenyl N-methyl carbamate, 2-isopropoxyphenyl N-methyl carbamate and S-methyl-15 N- (methylcarbamoyloxy) thioacetoimidate; N '- (2-methyl-4-chlorophenyl) -Ν, Ν-dimethylformamidine; 1,3-bis (carbamoylthio) -2- (Ν, Ν-dimethylamino) propane hydrochloride; other insecticides, microbial pesticides such as fungicides, nematocides, acaricides, plant growth regulators, B.T. and 20 B.M., insect hormone compounds, herbicides, fertilizers, and other agricultural chemicals. Furthermore, a synergistic effect can be expected by such mixing.

The aforementioned preparations generally contain 0.01 to 80 wt. %, preferably 0.05 to 60 wt. % of 25 the active ingredient (which includes other ingredients mixed therewith). However, since the amount and concentration of the active ingredient depends on the form of preparation, application time, application technique, application site, diseases and types of crop, they can be appropriately increased or decreased regardless of the aforementioned ranges.

Some examples of preparing compositions for the insecticides and acaricides of the invention will be discussed below.

Preparation Example 1 0.2 Parts of each of the compounds of the invention A to F are dissolved in kerosene and made up to 100 parts with kerosene to form the oil spray agent of each compound. to gain.

800 4278 40 - 15 -

Preparation example 2

0.25 parts of piperonyl butoxide is added to 0.05 parts of the compound A according to the invention, and this mixture is dissolved in kerosene and made up 5 to 100 parts with kerosene to obtain an oil spray.

Preparation example 3

To 20 parts of each of the compounds A to F of the invention is added 15 parts of Sorpol 10 3005X (a registered trademark of Toho Kagaku Co.) and 65 parts of xylene, and this mixture is stirred well to obtain a solution. An emulsifiable concentrate of each compound is thus obtained. Preparation example 4

15 to 60 parts of each of compounds A through F

according to the invention, 10 parts of Sorpol 3005X (a trademark of Toho Kagaku Co.) and 30 parts of xylene are added, and the mixture is stirred well to make a solution. An emulsifiable concentrate of each compound is thus obtained. Preparation example 5

To 10 parts of each of the compounds B and D of the invention is added 20 parts of S-421, 15 parts of Sorpol 3005X (the same as above) and 55 parts of xylene, 25 and this mixture is stirred well to obtain a solution. An emulsifiable concentrate of each compound is thus obtained.

Preparation Example 6 0.1 parts of the compound C of the invention, 0.2 parts of resmethrine, 7 parts of xylene and 7.7 parts of deodorized kerosene are mixed well to make a solution. This solution is applied in an aerosol container. After attaching a valve portion to the container, 85 parts of a propellant (liquefied natural gas) are introduced therein under pressure through the valve to obtain an aerosol. Preparation Example 7 '0.3 Part of Compound E of the Invention, 0.1 part of 3-phenoxybenzyl d-cis-trans-chrysanthemate, 7 parts of 40 xylenes, and 7.6 parts of deodorized kerosene are mixed 800 4278-16 - well to to make a solution. This solution is introduced into an aerosol container, and an aerosol is obtained in the same manner as in Preparation Example 6.

5 Preparation example 8

0.2 g of the d-trans chrysanthemum ester of allethrin is added to 0.15 g of each of the compounds C and E of the invention, and this mixture is dissolved in 20 ml of methanol. The solution is uniformly mixed with stirring with 99.65 g of a mosquito wrapping support containing Tabu powder, pyrethrum nut and wood powder in a ratio of 3: 5: 1, then the methanol is evaporated. 150 ml of water are added to the residue, and the mixture is kneaded well, formed into a mosquito wrap, and dried. Thus, the mosquito winding of each compound is obtained. Preparation example 9

0.05 g of 5-propargylfurfuryl dl-cis.trans-20 chrysanthemate and 0.1 g of BHT are added to 0.02 g of compound A of the invention, and the mixture is dissolved in an appropriate amount of chloroform. The solution is adsorbed uniformly in a 3.5 cm x 1.5 cm x 0.3 cm (thickness) filter paper. A fibrous fumigant intended to be heated on a hot plate is thus obtained.

Preparation example 10

To 20 parts of each of the compounds B and D of the invention are added 10 parts of phenitrothion (the same as above) and 5 parts of Sorpol SM-200 (a registered trademark of Toho Kagaku Co.), followed by careful mixing. The mixture is then mixed with 65 parts of a 300 mesh sieved diatomaceous earth while stirring well in a mortar.

In this way, a wettable powder of each compound is obtained.

Preparation example 11

2 parts of 3-methylphenyl N-methyl carbamate are added to 1 part of the compound A of the invention, and this mixture is dissolved in 20 parts of acetone. The solution is then mixed well with 79 parts of 800 42 78-17 - a 300 mesh sieved talc while stirring well in a mortar, then the acetone is removed by evaporation to give a dusting powder.

5 Preparation example 12

To 3 parts of each of the compounds A and B of the invention are added 5 parts of Toyolignin CT (a registered trademark of Toyo Spinning Co.) and 92 parts of GSM Clay (a registered trademark of Zieklite Mining Co.), and the mixture is mixed well with stirring in a mortar.

The mixture is then mixed well with water on a 10% basis, granulated by a granulator and dried in air. Thus, a grain preparation of each compound is obtained. Preparation Example 13 0.1 Part of Compound D of the Invention, 0.2 Part of the d-cis.trans Acid Isomer of Phenothrine, 11.7 Parts of Deodorized Kerosene, and 1 Part of Atmos 300, 20 an Emulsifier (Registered Trademark of Atlas

Chemical Co.), then emulsified with the addition of 50 parts of pure water. The emulsion is then applied to an aerosol container along with 35 parts of a 3: 1 mixture of deodorized butane 25 and deodorized propane to provide a water based aerosol.

The insecticidal activity of the esters according to the invention will now be explained in more detail by means of the following application examples.

Test Example 3.5 Milliliters of each of the oil sprays obtained in Preparation Examples 1 and 2 were sprayed according to the Campbell turntable method (Soap and Sanitary Chemicals, Vol. 14, No. 6, 119 (1938)), 35 using 100 house flies (Musea domestica) per group. The adult houseflies were exposed to the falling fog for 10 min. In the following day, at least more than 80% of the houseflies were killed. Test Example 4 40 The emulsifiable concentrate obtained in 8004273-18 Preparation Example 3 was diluted 100,000 times with water. 200 milliliters of the solution was placed in a 300 milliliter beaker, and 30 adult northern house mosquito larvae (Culex pipiens pallens) were released therein. In any case, the next day, more than 90% of the larvae were killed.

Test example 5

The insecticidal activity on adult houseflies (Musea domestica) of each aerosol, obtained in the preparation examples 6, 7 and 13, was tested by the aerosol test method (Soap and Chemical Specialties,

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Blue Book, 1965), using a (6 ft) Peet Grady's room. As a result, more than 80% of the flies were precipitated with each aerosol 15 min after spraying, and more than 70% of the flies were killed the following day.

Test example 6

About 50 northern house mosquitoes, female adults (Culex pipiens pallens) were released.

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20 in a (70 cm) glass chamber, in which a battery-type small electric fan (blade diameter 13 cm) was placed and powered.

0.1 Grams of each of the mosquito coils obtained in Preparation Example 8 was lit at one end 25 and placed in the center of the bottom of the chamber.

With each spiral of spirits, more than 90% of the mosquitoes could be deposited within 20 minutes and more than 80% of the mosquitoes could be killed the next day.

Test Example 7 About 50 adult houseflies (Musea domestica) 3 were released into a (70 cm) glass chamber in which a battery-type small electric fan (blade diameter 13 cm) was arranged and driven.

The heating perfume, obtained in Preparation Example 9, was placed on a hot plate in the chamber and evaporated. More than 90% of the flies could be knocked down within 20 minutes.

Test example 8

About 20 rice seedlings were grown to 40 at a 3-4-leaf stage in a 10 cm diameter flower pot, 800 42 78 - 19 - and the dusting powder obtained in Preparation Example 11 was sprayed at 3 kg / 10 are by from a clock atomizer. After spraying, the pot was covered with a wire net, and 20 to 30 green rice-5 grasshoppers, adult specimens (Nephotettix cincticeps) were released underneath. After 24 hours the dead and live specimens were counted, and as a result the mortality rate was found to be more than 80%.

Test Example 9 10 liters of water were placed in a 14 liter polypropylene bucket, and 1 g of each of the granulates obtained in Preparation Example 12 was added thereto. After 1 day, about 100 fully grown northern house mosquito larvae (Culex pipiens pallens) were released into the water. The dead and live were counted, and as a result it was found that more than 90% of the larvae could be killed within 24 hours in any case.

- conclusions - 800 42 78

Claims (6)

A new carboxylic acid ester, characterized in that it has a structural formula according to formula 1, wherein X is a chlorine, bromine or fluorine atom. Carboxylic acid ester according to claim 1, characterized in that it consists of (+) - 2-methyl-3-21-propynylcyclopent-2-en-4-on-1-yl (+) - 2,2-dimethyl -3-cis, trans-21,2'-dichlorovinylcyclopropane carboxylate. Carboxylic acid ester according to claim 1, characterized in that it consists of (+) - 2-methyl-3-2'-propynylcyclopent-2-en-4-on-1-yl (+) - 2,2- dimethyl-3-trans-21,21-difluorovinylcyclopropane carboxylate. Carboxylic acid ester according to claim 1, characterized in that it consists of (+) - 2-methyl-3 -21-propynylcyclopent-2-en-4-on-1-yl (+) - 2,2-dimethyl- 3-cis-2 ', 2'-dibromovinylcyclopropane carboxylate. A process for producing a carboxylic acid ester according to any one of the preceding claims, characterized by reacting a carboxylic acid of the formula 2, wherein X is a chlorine, bromine or fluorine atom, with an alcohol or a reactive derivative thereof with formula 3, wherein A is a hydroxyl group or a tosyloxy group. 6. Insecticidal composition or preparation, which as active ingredient contains an insecticidally effective amount of a carboxylic acid ester according to any one of claims 1 to 4 and an inert carrier. 800 42 78 CH2 hc Ξ c - ch2 f I I. X \ / —OC-C-C-C = cA yi I v ^ cA / \ CH3 CH3 (1) Η H 1. x HOC -C-C-C = C (2)