KR820000325B1 - Process for the preparation of cyclopropane thiocarboxylic acid ester and use there of as miticides - Google Patents

Abstract

Title compds. I(R = halo, C1-4 alkyl; m = 0-1; n =0-3). useful as acaricides and herbicides, were prepd. by reacting cyclopropane carboxylic chloride (II) and mercaptane (III) in inactive org. solvent. thus, 4.0 g 4-chlorobenzylmercaptane and 2.6 g cyclopropane carboxylic chloride were stirred in 25 ml benzene and mixed with 10ml benzene contg. 2.6 g Et3N to give 4-chlorobenzyl cyclopropane thiolcarboxylic ester salt.

Description

Preparation of cyclopropane thiolcarboxylic acid esters effective as a tick insecticide

The present invention relates to a method for producing cyclopropane thiolcarboxylic acid esters having a novel structural formula [I] effective as a tick insecticide. According to the present invention, it was found that S-benzyl and phenylthiomethyl cyclopropane thiolcarboxyl ester salts having the following general structural formulas are very effective as tick insecticides and have little or no toxicity to plants.

Wherein R is selected from the group consisting of halogen and lower alkyl having 1-4 carbon atoms, m is 0 or 1 and n is 0,1,2 or 3;

The term "halogen" includes fluorine, chlorine, cancellation and iodine, with chlorine being particularly preferred.

Lower alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl and tertiary butyl.

The compound of the present invention having the above structural formula [I] comprises a mercaptan having a cyclopropane carboxylic acid chloride having the following structural formula [II] having the following structural formula [III] having almost the same molecular weight, and from room temperature to reflux temperature It can be prepared by reacting in an inert solvent in the presence of an acid acceptor at a temperature within the range of.

The reaction is preferably carried out in an inert organic solvent such as benzene, toluene, methylene chloride, glycol dimethyl ether and the like. The reaction temperature is sufficient to reach a solvent boiling point at about 0 ° C, but room temperature is preferred for convenience. Acid acceptors that can be used include tertiary amines such as triethylamine, pyridine and dimethylaniline.

Another method of preparing the compounds of the present invention is to react the cyclopropane thiolcarboxylate salts of alkali metal salts with a suitable halogenated benzyl or halogenated phenyleomethyl.

The following examples show the pesticidal activity against typical compound preparations of the present invention and their ginsengs.

Example 1

This example illustrates the preparation of 4-chlorobenzyl cyclopropane thiolcarboxyl ester salt.

A solution of 4.0 g (0.025 moles) of 4-chlorobenzyl mercaptan and 2.6 g (0.025 moles) of cyclopropane carboxylic acid chloride in 25 ml of benzene was prepared and stirred, followed by 2.6 g of triethylamine in 10 ml of benzene. The dissolved product is added dropwise to the reaction mixture. The reaction mixture is refluxed for two hours, cooled, washed with water and dried over anhydrous magnesium sulfate. By filtering the product and removing volatiles, 4.7 g of liquid product with refractive index N _D ³⁰ -1.5549 are obtained. The structure of the product ie 4-chlorobenzyl cyclopropane thiolcarboxylic acid ester is confirmed by infrared and NMR analysis.

Example 2

This example illustrates the preparation of 4-chlorophenylthiomethyl cyclopropane thiolcarboxylic acid ester.

A solution of 2.1 g of sodium hydrogen sulfide dissolved in 15 ml of ethanol was cooled in an ice water bath to about 4 ° C., and then 2.6 g (0.025 mol) of cyclopropane carboxylic acid chloride was added thereto. While the temperature rises to 36 ° C., the reaction mixture is cooled to 5 ° C. while stirring. After the opening, 4.8 g (0.025 mol) of 4-chlorophenyl thiomethyl chloride are added and the temperature is allowed to rise to room temperature. 10 g (0.025 mol) of sodium hydroxide (2 g of 5% aqueous sodium hydroxide solution in 10 ml of water) are added. The temperature rises to 50.5 ° C. and is left to cool to room temperature. Then, about 15 ml of methylene dichloride is added. The reaction mixture is washed three times with a 10% aqueous solution of sodium bicarbonate and dried over anhydrous magnesium sulfate. Filtration of the product and removal of volatiles yielded 5.0 g of a liquid product with a refractive index N _D ³⁰ -1.5770. The structure of the product, ie, 4-chlorophenylthiomethyl cyclopropane thiolcarboxylic acid ester, is confirmed by infrared and NMR analysis.

Other compounds that can be made with the present invention can be made in a similar manner using suitable starting materials, which will be apparent to those skilled in the art.

The following table exemplarily shows compounds falling within the scope of the present invention. Compounds are numbered for convenience and are used herein intact.

TABLE 1

Insecticidal activity against Tetranychus urticae of the compounds of the present invention was tested as follows.

About 10cm of stalked Gangnam bean plants were transplanted into a 3-inch earthenware bowl containing sand mixed loam and completely covered with two spotted mites that had no distinction between age and sex. After 24 hours, reverse the mite-covered plant and soak the test compound in an aqueous solution of 50-acetone 50 for 2-3 seconds. The treated plants were placed in the greenhouse for 7 days, and the mortality of the adult and hatched larvae from the eggs attached to the plants was measured. Test concentrations range from 0.05% to 50% mortality.

TABLE 2

＞ = greater than

As shown in the data, the compounds of the present invention can be used to effectively inhibit ticks. It is particularly effective as a dispersing agent that prevents hatching of eggs.

Toxicity to plants of the representative compounds of the present invention was tested and compared with that of the corresponding phenyl compounds. Test compounds were S-3,4-dichlorobenzylcyclopropane thiolcarboxylic acid ester, S-3,4-dichlorophenylcyclopropane thiolcarboxylic acid ester, S-2-chlorobenzyl cyclopropane thiolcarboxylic acid ester and S 2-chlorophenyl cyclopropane thiolcarboxylic acid ester.

In these tests, standard tests indicating chemical manufacturing activity were taken. The test is as follows.

[Beef germination test]

(소르비탄 모노로우레이트의 폴리옥시 에틸렌 유도체)을 함유하는 3ml의 아세톤을 가하여 화합물을 녹인다. 만약 그 물질이 아세톤에 녹지 않을 경우에는 물, 알코올 또는 디메틸포름아미드(DMF) 같은 다른 용매를 대신 사용한다. DMF를 사용하는 경우에는 0.5ml 또는 그 이하 양을 사용하여 화합물을 녹이고, 3ml로 양을 늘이기 위해서는 딴 용매를 사용한다. 작은 스티로폼 상자에 담긴 흙에 풀씨를 뿌린 하루후에 3ml의 이용액을 고르게 살포한다. 살포할 때에는 152호 데빌비스 분무기로 평방인치당 5파운드의 압축공기를 이용하였다. 사용율은 에어커당 8파운드이고 살포량은 에어커당 143갈론이다.20 mg of test compound is placed on glassine for analysis. Place the paper with the compound in a 30 ml wide mouth bottle, 1% Tween 20

3 ml of acetone containing (polyoxy ethylene derivative of sorbitan monolaurate) is added to dissolve the compound. If the substance is insoluble in acetone, use another solvent, such as water, alcohol or dimethylformamide (DMF) instead. If DMF is used, dissolve the compound in an amount of 0.5 ml or less, and use another solvent to increase the amount to 3 ml. After a day of sowing grass in a small styrofoam box, apply 3 ml of solution evenly. When spraying, 152 Devilvis sprayers used 5 pounds of compressed air per square inch. The utilization rate is 8 pounds per acre and the spread rate is 143 gallons per acre.

The day before the treatment, a 7-inch-wide, 5-inch-deep, 2.74-inch fiber box is filled with 2 inches of high-quality soil, and six seeds of grass are sprayed, one for each row across the box. Cover the soil so that the seeds are covered 0.5 inch thick.

Seeds used are hairy king buckwheat, watergrass, red rooted tuna, Indian mustard, dried swim, and green beans. Sow enough seeds so that after germination, you will have 20-50 livestock per row, depending on their size.

After treatment, place the crates in a greenhouse at 70-85 ° F and water them with a sprinkler.

After 2 weeks of treatment, the damage or inhibition is measured by comparison with the untreated control plants of the same age. The ratio is recorded as 0 for no damage and 100% for complete death.

[Weeding test after germination]

을 함유하는 5ml의 아세톤에 녹여 5ml의 물에 용해한 것을 152호 데빌비스분무기를 써서 평방인치당 5파운드의 공기압력으로 그 군엽(群葉)에 살포한다. 살포농도는 0.2%이며, 그 율은 에어커당 8파운드 살포량은 에어커당 476갈론이다. 처리 14일후에 그 손상도를 기록하는데 평가방법은 발아전 시험 때와 같다. 이 시험결과를 표 3에 표시한다.Six seeds, including hairy king buckwheat, watergrass, nectarine, mustard, dried leaves, and green beans, are sown in the same box as in the pre-germination test. Place the crates in a 70-85 ° F greenhouse and water them with a sprinkler every day. 10-14 days after sowing, the first leaf of this legume spreads well and reaches the first trimester.

It was dissolved in 5 ml of acetone containing and dissolved in 5 ml of water, and then sprayed onto the leaf by using a No. 152 Devilvis sprayer at an air pressure of 5 pounds per square inch. The spraying concentration is 0.2% and the rate of 8 pounds per acre is 476 gallons per acre. The damage is recorded after 14 days of treatment, and the evaluation method is the same as in the pre-germination test. The test results are shown in Table 3.

TABLE 3

CG-Wild King's WW-Watergrass PW-Red Root Mint

CD-dried dried MD-Indian mustard PB-staining

As seen from the above results, the S-benzyl cyclopropane thiolcarboxylic acid esters of the present invention are significantly less toxic than the S-phenyl compound used. Therefore, it is particularly effective in suppressing ticks attached to the plant leaf.

The compounds of the present invention are usually used in the form of containing the compound and an inert carrier in a place where suppression of ticks is desired, and usually takes the form of powder, wet powder, granule, solution, emulsifier and the like.

The powder is a powder composition free of flow which contains the pesticide compound in a specific carrier. The particle size of the carrier is generally in the range of 30-50 microns.

Examples of suitable carriers are talc, bentonite, diatomaceous earth, pyrophyllite and the like. If necessary, anticaking agents may be added. This composition usually contains up to 50% of the active ingredient.

Wet powder is a fine particle composition in which a specific carrier containing a pesticide compound is mixed with one or more surfactants. The surfactant promotes the rapid diffusion of the powder in the liquid medium, making it a stable spray suspension.

A wide range of surface active agents are used, for example, alkali metal salts of long chain aliphatic alcohols and sulfated aliphatic alcohols, salts of sulfonic acids, esters of long chain fatty acids and polyhydric alcohols.

A list of surfactants suitable for agriculture can be found in Pesticide Formulations (marcel Dekker Inc., N.Y. 1973), pp. 79-84 by Wade Schönenberg.

Granules are those in which a pesticide compound is contained in a specific inert carrier with a diameter of 1-2 mm, which is made by spraying a granular carrier with a solution of the active ingredient dissolved in a volatile solvent. Suitable carriers for granulation are clay, vermiculite, sawdust, granulated coal and the like.

Pesticide compounds may also be used in the soil in the form of solutions dissolved in a suitable solvent. Commonly used solvents for pesticide formulations include petroleum, fuel oil, petroleum oils having a boiling range above xylene and aromatic petroleum oils rich in modified naphthalene.

Emulsified concentrates consist of a useful insecticide solution and an emulsifier, which are diluted with water before use to form an emulsion of oil droplets. The emulsifiers used are usually mixtures of anionic and nonionic surfactants. If desired, other additives such as diffusion electrodeposition agents can be added.

The composition uses an effective insecticide in a place where the mite is suppressed and used as a general spreading device as a solution or a suspension. The solution or suspension contains about 0.01-5.0% by weight of the pesticide, but preferably about 0.1-2.0%.

Claims (1)

Cyclopropane carboxylic acid chloride having the following structural formula [II] is inert in the presence of a tertiary amine having a mercaptan having the following structural formula [III] having substantially the same molecular weight and a temperature within a range from room temperature to reflux temperature. The manufacturing method of cyclopropane thiol carboxylic acid ester which has the following structural formula [I] useful as a tick insecticide formed by making it react in an organic solvent.

Wherein R is selected from the group consisting of lower alkyl having 1-4 carbon atoms of halogen, m is 0 or 1 and n is 0, 1, 2 or 3;