KR920005412B1 - 1,2,4-oxadiazole derivative substituted 5-fluoromethy group - Google Patents

Abstract

5-Fluoromethyl substd.1,2,4-oxadiazole derivs. of formula (I) are nw. In (I), R=alkoxymethyl, lower alkyl amino carbonyl thiomethyl, alkoxy phosphonyl thiomethyl, H, halogen or alkyl substd. Percarbonyl oxymethyl, H, halogen or nitro substd. phenylmethyl, H, halogen, alkyl, alkoxy or thioalkoxy substd. phenoxymethyl, H, halogen or alkyl substd. thiophenoxymethyln pyridine thiomethyl, pyrimidine thiomethyl or pyrazole thiomethyl. The cpds. (I) are pref. 3-(2'-chlorophenyl)-5-fluoromehyl- 1,2,4oxadiazole, 3- (4'- bromophenyl) methyl- 5- fluoromethyl- 1,2,4oxadiazole or 3-(4'- chlorophenoxy) methyl-5- fluoromethyl- 1,2,4oxadiazole. (I) are useful as an insecticide.

Description

1, 2, 4-oxadiazole derivatives substituted with 5-fluoromethyl

The present invention relates to a process for the preparation of 1, 2, 4-oxadiazole derivatives substituted with 5-fluoromethyl of the general formula (I), which is useful as an insecticide.

Wherein R is alkoxymethyl, lower alkylamino carbonylthiomethyl, alkoxyphosphonylthiomethyl, hydrogen, halogen, phenylcarbonyloxymethyl substituted with alkyl, hydrogen, halogen, nitro-substituted phenyl, hydrogen, halogen, Nitro, alkoxy substituted phenylmethyl, hydrogen, halogen, alkyl group, alkoxy, thioalkoxy substituted phenoxymethyl, hydrogen, halogen, alkyl substituted thiophenoxymethyl, pyridinethiomethyl, pyrimidinethiomethyl, pyra Zolthiomethyl.

Since 1, 2, 4-oxadiazole-based compounds have been used as medicines such as anesthetics, analgesics, anti-inflammatory drugs, etc. of numerous compounds by the development of various synthetic methods and research on physiological activity since 1960.

Recently, organic compounds including heterocycles such as thiazole, thiadiazole, isoxazole, and pyrazole have been developed as fungicides, insecticides, herbicides, and the like. In particular, compounds in which 1, 2, 4-oxadiazole structures are substituted in the side chains of pyrethroid-based, organophosphorus-based and carbamate-based compounds, which are known as the main structures of insecticides, and 1, 2, 4- which have a novel insecticidal effect. Oxadiazole-based compounds are disclosed in the Federal Republic of Germany Patent No. 2,310,287, No. 2,312,453, No. 2,312,500, No. 2,343,548, No. 2,406,786, No. 2,451,588, No. 2,430,758, No. 2,620,615, No. 3,010,319,135, 3,010,319 Patents 3,856,897, 3,976,657, 4,134,985, 4,213,973, French Patent 2,154,279 and European Patent 0,325,336. Thus, 1, 2, 4-oxadiazole-based compounds are expected to be greatly expected as a pesticide, and is still under study in the field.

In order to be developed as a new insecticide, the insecticidal effect must be accurate, the crops must be harmless, and the stocks, fish poisons and residual toxicity must be low or free. It should also be low or selective against total and useful insects. Conventional pesticides have been somewhat problematic to be recognized as ideal pesticides as described above.

The present inventors have extensively studied and studied to solve the above-mentioned drawbacks. As a result, novel compounds of 1, 2 and 4-oxadiazole derivatives substituted with 5-fluoromethyl have excellent insecticidal and acaricidal effects and broad spectrum. It was found that the present invention was completed. In particular, it exhibits excellent insecticidal and acaricide effects on aphids and mites, and also has a good scattering effect on mites. In addition, moths and extinct species have a significant pesticidal effect.

It is a first object of the present invention to provide 1, 2, 4-oxadiazole derivatives substituted with 5-fluoromethyl of formula (I).

A second object of the present invention is to provide a method for preparing 1, 2, 4-oxadiazole derivatives substituted with 5-fluoromethyl of formula (I).

The third object of the present invention is as an insecticide, characterized in that it contains at least one compound selected from 1, 2, 4-oxadiazole derivatives substituted with 5-fluoromethyl of the general formula (I) as an active ingredient. To provide a use.

Hereinafter, the present invention will be described in detail.

Formula (I) compound of the present invention can be prepared according to the following methods. However, the present invention is not limited to these production examples.

Method 1

[Step 1]

The amide oxime of general formula (IV) is obtained by reacting the nitrile of general formula (II) with the free hydroxylamine obtained by neutralizing the hydrochloride salt or sulfate of hydroxylamine of general formula (III) with alkali. As a solvent used at this time, alcohol, water, etc. are preferable, You may use these individually or in combination of 2 or more types. As for reaction temperature, 0 degrees C or less is preferable.

[2 steps]

The amide oxime of formula (IV) and the acyl chloride of formula (V) prepared in step 1 were dried with acetone, acetonitrile, benzene, toluene, ethyl acetate, halogenated hydrocarbon, dioxane in the presence of organic or inorganic base. O-acylamide oxime of formula (VI) is prepared by reacting in a solvent such as, ether. Examples of the organic base include triethylamine and pyridine, and examples of the inorganic base include sodium carbonate and potassium carbonate. The reaction temperature is preferably from room temperature to 60 ℃ when using an organic base, the temperature of the boiling point of the solvent is preferred when using an inorganic base.

[3 step]

O-acylamide oxime of formula (VI) obtained in step 2 is subjected to ring-closure reaction in an organic solvent in the presence of a catalyst to prepare 1, 2, 4-oxadiazole derivatives of formula (VII). At this time, the catalyst used may be sodium methoxide, diethylamine, triethylamine, trifluoroboron ether (BF ₃ · Et ₂ O) and the like, acetone, alcohol, dioxane, toluene, etc. desirable. The reaction temperature is suitable for the boiling point of the solvent used, the reaction time is preferably 4 to 12 hours.

[4 steps]

1, 2, 4-oxadiazole derivatives of the general formula (VII) obtained in the above 3 step was reacted with alkali metal fluoride of the general formula (VIII) in the presence of a catalyst to 5-fluoromethyl of the general formula (IX) This substituted 1, 2, 4-oxadiazole derivative is prepared. At this time, acetonitrile is used as an organic solvent, and 18-crown ether is used as a catalyst. The reaction temperature is preferably the boiling point of the solvent, the reaction time is suitable 20 to 48 hours.

[5 steps]

1, 2 and 4-oxadiazole derivatives of the general formula (IX) obtained in step 4 are reacted with various kinds of electrophiles (X) to substitute the 5-fluoromethyl of the general formula (I). To prepare 4-oxadiazole derivatives. At this time, tetrahydrofuran (THF), dimethylaminoformaldehyde (DMF) and the like can be used as the organic solvent, the reaction temperature is preferably from room temperature to the boiling point of the solvent, the reaction time is suitable for 5 to 20 hours.

The method is represented by the following scheme.

Wherein R ¹ is alkoxy, lower alkylaminocarbonylthio, alkoxyphosphonylthio, hydrogen, halogen, phenylcarbonyloxy substituted with alkyl group, hydrogen, halogen, alkyl group, phenoxy substituted with thioalkoxy, hydrogen, halogen , Thiophenoxy, pyridinethio, pyrimidinethio, pyrazolethio substituted with an alkyl group, and M represents sodium (Na), potassium (K) or cesium (Cs).

Second method

[Step 1]

The amide oxime of the general formula (XII) is prepared by the same method as in the first method 1, using the nitrile of the general formula (XI) and the sulfate or nitrate of the hydroxylamine of the general formula (III).

[2 steps]

O-acylamide oxime of the general formula (XII) is prepared in the same manner as in step 1 of step 2 using the amide oxime of the general formula (XII) and the acyl chloride of the general formula (V) prepared in step 1 above.

[3 step]

O-acylamide oxime of Formula (XIII) prepared in step 2 was subjected to ring-closure reaction under a catalyst in the same manner as in Step 3 of Step 1 to prepare 1, 2, 4-oxadiazole derivatives of Formula (XIV). do.

[4 steps]

The 1, 2, 4-oxadiazole derivatives of the general formula (XIV) prepared in step 3 were reacted with the alkali metal fluoride of the general formula (VIII) by the method according to the first method 4 step (I). To prepare 1, 2, 4-oxadiazole derivatives substituted with 5-fluoromethyl.

The method is represented by the following scheme.

Wherein R ² represents hydrogen, halogen, nitro-substituted phenyl, hydrogen, halogen, nitro, alkoxy-substituted phenylmethyl, and M represents potassium (K) or cesium (Cs).

Third method

[Step 1]

The nitrile of formula (XVI) is prepared by reacting a nitrile of formula (II) with a substituted phenol of formula (XV) in a solvent such as acetone, acetonitrile or ether dried in the presence of an organic or inorganic base. Examples of the organic base include triethylamine and pyridine, and examples of the inorganic base include sodium carbonate, potassium carbonate, potassium hydroxide and sodium hydroxide. The reaction temperature is preferably at the boiling point of the solvent when the organic base is used, and is preferably at room temperature or the boiling point of the solvent when the inorganic base is used.

[2 steps]

The free hydroxylamine obtained by neutralizing the hydrochloride or sulfate salt of the nitrile of general formula (XVI) and the hydroxylamine of general formula (III) prepared in step 1 with alkali was prepared by the method of step 1 of step 1 in the general formula (XVII). Amidoxime is obtained.

[3 step]

Preparation of O-acylamide oxime of the general formula (XVII) using the same method as in the second step 1 using the amide oxime of the general formula (XVII) and the acyl chloride of the general formula (V) prepared in step 2 do.

[4 steps]

O-acylamide oxime of formula (XVII) prepared in step 3 was subjected to ring-closure reaction under a catalyst in the same manner as in step 3 of step 1 to prepare 1, 2, 4-oxadiazole derivatives of formula (XIX). do.

[5 steps]

The 1, 2 and 4-oxadiazole derivatives of the general formula (XIX) prepared in step 4 were reacted with the alkali metal fluoride of the general formula (VIII) by the method according to the first method 4 step (I). To prepare 1, 2, 4-oxadiazole derivatives substituted with 5-fluoromethyl.

The method is represented by the following scheme.

Wherein X represents hydrogen, halogen, an alkyl group, alkoxy, thioalkoxy and M represents potassium (K) or cesium (Cs).

In the above 1, 2, 3 method, the amide oxime, O-acylamide oxime and final product 1, 2, 4-oxadiazole derivatives obtained by each process are distilled, crystallized and chromatographic depending on the physical properties of each compound. The compounds were separated and purified according to methods commonly performed in the art, and the identification of the compounds was performed using IR, NMR, mass spectrometry, and the like.

As the following examples, the present invention will be described in more detail.

Example 1

(1) Synthesis of chloroacetamide oxime.

6.95 g (0.1 mol) of hydroxylamine hydrochloride and 10.6 g (0.1 mol) of sodium carbonate were dissolved in 25 ml of water, and 7.55 g (0.1 mol) of chloroacetnitrile was slowly added dropwise while maintaining the temperature of the reaction solution at 0 ° C or lower. After stirring for 30 minutes, the reaction solution was extracted twice with 50 ml of ether, and the organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated at room temperature to obtain 7.6 g of white acicular crystal chloroacetamide oxime. (Yield: 70%)

NMR (CDC ₃ TMS) δ; 8.4 (b, 1H), 5.3 (b, 2H), 4.0 (s, 2H)

(2) Synthesis of O-chloroacetylchloroacetamide oxime.

To 100 ml of methylene chloride, 7.1 g (0.065 mol) of chloroacetamide oxime prepared in (1) and 9.1 ml (0.065 mol) of triethylamine were added, and 5.2 ml of chloroacetyl chloride was maintained while maintaining the temperature of the reaction solution at 5 ° C or less. 0.065 mol) was slowly added dropwise. After stirring for 1 hour, the reaction solution was washed with 100 ml of water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography (eluent, ethyl acetate: hexane = 1: 1) to give 10.2 g of a white solid. (Yield: 85%)

(3) Synthesis of 3.5-dichloromethyl-1, 2, 4-oxadiazole.

To 100 ml of dried toluene, 10.0 g (0.054 mol) of O-chloroacetylchloroacetamide oxime prepared in (2) and 0.28 g (0.002 mol) of boron fluoride and ether were added, and 1 ml of water produced under reflux for 4 hours was heated. Was removed. The residue obtained by concentrating the reaction solution under reduced pressure was distilled under reduced pressure to obtain 7.2 g of a liquid having a temperature of 86 to 88 ° C. at 3 mmHg. (Yield: 80%)

(4) Synthesis of 3-chloromethyl-5-fluoromethyl-1, 2, 4-oxadiazole.

In 100 ml of dried acetonitrile, 7.0 g (0.042 mol) of 3,5-dichloromethyl-1, 2, 4-oxadiazole prepared in (3) was dissolved, cesium fluoride 19.3 (0.13 mol) and a phase transfer catalyst. 18-crown-6 ether (0.05 g) was added thereto, and the mixture was heated to reflux for 20 hours. The reaction solution was cooled to room temperature and filtered, and the residue obtained by concentrating the filtrate under reduced pressure was vacuum distilled to obtain 4.55 g of a liquid having a temperature of 64 to 66 ° C. at 2 mmH. (Yield: 72%)

(5) Synthesis of 3-methoxymethyl-5-fluoromethyl-1, 2, 4-oxadiazole.

To 50 ml of acetonitrile 0.3 g (0.002 mol) of 3-chloromethyl-5-fluoromethyl-1, 2, 4-oxadiazole prepared in (4), 0.064 g (0.002 mol) of methanol, 0.276 g of potassium carbonate ( 0.002 mole) was added and heated to reflux for 6 hours. The reaction mixture was concentrated, extracted with 50 ml of ethyl acetate, the organic layer was dried over anhydrous sodium sulfate to remove the solvent, and the residue was purified by column chromatography (eluent, ethyl acetate: hexane = 1: 4) to obtain an oily substance 0.21. g was obtained. (Yield: 72%)

Elemental Analysis (C ₅ H ₇ FN ₂ O ₂ )

Theoretic value: C; 41.11, H; 4.79, N; 19.18

Found: C; 40.93, H; 4.68, N; 19.05

NMR (CDCl ₃ · TMS) δ; 5.5 (d, 2H), 5.3 (s, 2H), 2.3 (s, 3H)

EXAMPLES 2-10

Prepared using the method of Example 1 from each substituted thio anion or substituted phenyl, benzyl, pyridine acid. Each compound was purified by column chromatography, and the physical and elemental analysis values are shown in Table 1.

Example 11

(1) Synthesis of 2-chlorophenylacetamide oxime.

Dissolve 8.3 g (0.12 mole) of hydroxylamine hydrochloride and 10.1 g (0.12 mole) of sodium carbonate in 500 ml of water, add 13.7 g (0.1 mole) of 2-chlorophenylacetnitrile in 100 ml of ethyl alcohol, and then heat for 6 hours. It was refluxed. The reaction mixture was concentrated under reduced pressure, extracted with 100 ml of ethyl acetate, dried over anhydrous magnesium sulfate, the solvent was removed, and the mixture was washed with benzene to obtain 13.6 g of a product. (Yield: 80%)

(2) Synthesis of 3- (2'-chlorophenyl) -5-chloromethyl-1, 2, 4-oxadiazole.

12.5 g (0.073 mol) of 2-chlorophenylacetamide oxime prepared in (1) was added to 100 ml of 1,4-dioxane, and 8.25 g (0.073 mol) of chloroacetyl chloride was maintained while maintaining the temperature of the reaction solution at 0 ° C. Slowly added dropwise. Chloroacetyl chloride was completely added, and then the temperature of the reaction solution was warmed to 70 ° C, 0.14 g (0.001 mol) of boron fluoride ether was added, and the mixture was heated to reflux for 5 hours. The solvent was evaporated under reduced pressure, extracted with 100 ml of ethyl acetate, dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography to obtain 11.7 g of a product. (Yield: 70%)

(3) Synthesis of 3- (2'-chlorophenyl) -5-fluoromethyl-1, 2, 4-oxadiazole.

To 200 ml of dried acetonitrile, 10.6 g (0.046 mol) of 3- (2'-chlorophenyl) -5-chloromethyl-1, 2,4-oxadiazole prepared in (2) and 20.0 g of cesium fluoride ( 0.138 mol) was added and heated to reflux for 16 hours. The reaction mixture was washed with water, and the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluent, ethyl acetate: hexane = 1: 4) to obtain 4.89 g of a product. (Yield 50%)

Elemental Analysis (C ₉ H ₆ ClFN ₂ O)

Theoretic value: C; 50.85, H; 2.82, N; 13.18

Found: C; 50.73, H; 2.78, N; 13.06

NMR (CDCl ₃ · TMS) δ; 7.5-6.9 (m, 4H), 5.6 (d, 2H)

Examples 12 to 25

Prepared using the method of Example 11 from each substituted phenyl or phenylmethylnitrile. Each compound was purified by column chromatography, and the physical and elemental analysis values are shown in Table 1.

Example 26

(1) Synthesis of Phenoxy Acetonitrile.

9.41 g (0.1 mol) of phenol, 7.55 g (0.1 mol) of chloroacenitrile, 13.82 (0.1 mol) of potassium carbonate, and 0.25 g (0.0015 mol) of potassium iodide were mixed with 100 ml of acetone and heated to reflux for 24 hours. After completely concentrating the reaction solution, 100 ml of water was added, followed by dry concentration from an organic layer obtained by extracting twice with 100 ml of ether to obtain 12.6 g of a product. Purification by column chromatography (eluent, benzene: hexane = 7: 3) gave 9.6 g of phenoxy acetonitrile. (Yield: 71.9%)

(2) Synthesis of phenoxyacetamide oxime.

4.17 g (0.06 mol) of hydroxylamine hydrochloride and 6.36 g (0.06 mol) of sodium carbonate were dissolved in 30 ml of water, and 8.0 g (0.06 mol) of phenoxyacenitrile prepared in (1) was dissolved in 50 ml of ethyl alcohol, and then added. The mixture was stirred and heated to reflux for 6 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the residue was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed. The residue was purified by column chromatography (eluent, ethyl acetate: hexane = 1: 1). Purification with 1) afforded 8.0 g of phenoxyacetamide oxime. (Yield: 81%)

(3) Synthesis of O-chloroacetylphenoxyacetamide oxime.

To 50 ml of methylene chloride, 3.32 g (0.02 mol) of phenoxyacetamide oxime prepared in (2) was mixed, 2.06 g (0.02 mol) of chloroacetyl chloride, and 2.02 g (0.02 mol) of triethylamine were stirred at room temperature for 30 minutes. . The reaction mixture was washed with 100 ml of water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography (eluent, ethyl acetate: hexane = 1: 2) to give 4.4 g product (yield: 90%).

(4) Synthesis of 3-phenoxymethyl-5-chloromethyl-1, 2, 4-oxadiazole.

3.63 g (0.015 mol) of O-chloroacetylphenoxyacetamide oxime prepared in (3) was dissolved in 50 ml of 1,4-dioxane, and 0.14 g (0.001 mol) of boron fluoride ether was added thereto for 6 hours. Heated to reflux. The reaction mixture was filtered and the obtained organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography (eluent, ethyl acetate: n-hexane = 1: 4) to obtain 2.35 g of an oily substance. (Yield: 70%)

(5) Synthesis of 3-phenoxymethyl-5-fluoromethyl-1, 2, 4-oxadiazole.

To 20 ml of dried acetonitrile, 1.1 g (0.0049 mol) of 3-phenoxymethyl-5-chloromethyl-1, 2, 4-oxadiazole prepared in (4) was added, and 1.55 g (0.012 mol) of cesium fluoride was added. ) Was added and then heated to reflux for 16 hours. The reaction solution was concentrated, extracted with 30 ml of ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed. Then, the mixture was purified by column chromatography (eluent, ethyl acetate: hexane = 1: 4) to obtain 0.62 g of an oily substance. (Yield 60.8%)

Elemental Analysis (C ₁₀ H ₉ FN ₂ O ₂ )

Theoretic value: C; 57.71, H; 4.32, N; 13.46

Found: C; 57.55, H; 4.25, N; 13.38

NMR (CDCl ₃ · TMS) δ; 7.45-6.80 (m, 5H), 5.47 (d, 2H), 5.13 (s, 2H)

[Examples 27-52]

Prepared using the method of Example 26 from each substituted phenol. Each compound was purified by column chromatography, and the physical and elemental analysis values are shown in Table 1.

[Examples 53 to 62]

Prepared using the method of Example 1 from each substituted benzyl, pyridine, diazine, pyrazolethio anion. Each compound was purified by column chromatography, and the physical and elemental analysis values are shown in Table 1.

Example 63

Synthesis of 3- (4'-chloro) phenylsulfonylmethyl-5-fluoromethyl-1, 2, 4-oxadiazole.

1.5 g (0.0058 mol) of 3- (4′-chloro) thiophenoxymethyl-5-fluoromethyl-1, 2,4-oxadiazole and 2.07 g of m-chloroperbenzoic acid prepared in Example 55 Was added to 50ml of dichloromethane and stirred at room temperature for 5 hours. The reaction solution was washed with saturated sodium hydrocarbon and 10% sodium sulfite, extracted with dichloromethane, and dried over anhydrous sodium carbonate to liberate the solvent. The residue obtained was purified by column chromatography (eluent, ethyl acetate: hexane = 1: 1) to obtain 1.53 g of a product. (Yield: 91%)

Elemental Analysis: C ₁₀ H ₈ ClFN ₂ O ₃ S

Theoretic value: C; 41.32, H; 2.75, N; 9.64

Found: C; 41.12, H; 2.81, N; 9.55

NMR (CDCl ₃ · TMS) δ; 8.0-7.6 (q, 4H), 5.7 (d, 2H), 4.9 (s, 2H)

Insecticidal activity test for the compound of the present invention was carried out by the method described below.

TABLE 1

Insecticidal activity test

1. Light Crush

Roots of six 4-5 cm Dongjin rice seedlings are rolled with cotton wool and placed in a test tube (ø3 x 15 cm) containing about 2 ml of water. Twenty young adult rice larvae after 3 to 5 days of fable are captured by a suction tube and radioinoculated in vitro. Spray the test solution with a certain concentration using a micro spreader. Cover the tube inlet with radiation and store it in a thermostat at 25 ° C to investigate mortality after 24 and 48 hours. Insecticidal test results of the compounds for rice hoppers are shown in Table 2.

2. Chinese cabbage moth

Cabbage leaves of uniform growth are cut to 5 cm in diameter, immersed in the test solution for 30 seconds, and then scabies. The treated leaflets are placed in a Petri dish (? 5 × 1 cm) covered with filter paper and inoculated with 10 larvae of three larvae. The test container is covered with a lid and stored in a 25 ℃ thermostat, and the mortality rate is examined after 24 and 48 hours. Insecticidal test results for the cabbage moth of the compounds are shown in Table 2.

3. Tobacco Seminar Room

Cabbage leaves of uniform growth are cut to 5.5 cm in diameter, and then immersed in the test solution for 30 seconds and then scabies. The treated leaves were placed in a Petri dish (ø5.5 × 2 cm) with filter paper, and inoculated with 10 larvae of three larvae. The test container is covered with a lid and stored in a 25 ℃ thermostat, and the mortality rate is examined after 24 and 48 hours. Insecticidal test results for the tobacco macromolecular moth of the compound are shown in Table 2.

4. Peach or Aphid

A tobacco leaf piece of 5.5 cm in diameter is immersed for 30 seconds in the test solution liquid and then air dried. The treated leaves were placed in a plastic petri dish (ø5.5 x 2 cm) with filter paper and inoculated with 20 insects. Test containers should be capped and stored at 25 ° C. incubator for 25 and 48 hours to examine mortality. Insecticidal test results for the peach or aphid of the compounds are shown in Table 2.

5. Rice weevil

Twenty test specimens 1 to 2 weeks after allegory are captured by a suction tube, placed in a test tube (ø1 × 5 cm), and the test tube is immersed in water at 0 ° C. and paralyzed at low temperature. The test insect is placed in a plastic petri dish (ø5 x 1 cm) together with 1 g of white rice, and a predetermined concentration of the test reagent solution is sprayed using a micro spreader. The mortality rate is examined after 24 and 48 hours in a 25 ° C thermostat. The results of the killing test of the compounds for rice weevil are shown in Table 2.

6. Red Mosquito

In a 100 ml beaker, 50 ml of distilled water and a predetermined concentration of the test reagent solution are diluted, and 20 larvae of the larvae 3 are inoculated. The mortality rate is examined after 24 and 48 hours in a 25 ° C thermostat. Insecticidal test results for the red conglomerates of the compounds are shown in Table 2.

7. Spotted Love

Place cotton wool on a plastic Petri dish (ø5.5 x 2 cm), fill it with an appropriate amount of water, place a 2.5 cm diameter leaf on it, and inoculate 30 adults with a thin brush. Spray the test solution with a certain concentration using a micro spreader. The mortality rate is examined after 24 and 48 hours in a 25 ° C thermostat. In the sallan test, 10 adult adults were inoculated on 2.5 cm diameter Gangnam leaf leaves, spawned for 24 hours, the strata were removed, the pre-density was examined, and then submerged in the test solution for 10 seconds. After treatment, it is stored in a thermostat at 25 ° C and the hatching inhibition rate is examined after 7 days. The insecticidal test results for spotted mites of the compounds are shown in Table 2, and the results for the sallan test are shown in Table 3.

The abbreviations of the test insects used in the pesticidal activity test as described above are shown in Table 4.

TABLE 2

TABLE 3

TABLE 4

Claims (10)

1, 2, 4-oxadiazole derivatives substituted with 5-fluoromethyl of the following general formula (I).

Wherein R is alkoxymethyl, lower alkylamino carbonylthiomethyl, alkoxyphosphonylthiomethyl, hydrogen, halogen, percarbonyloxymethyl substituted with alkyl group, hydrogen, halogen, nitro substituted phenylmethyl, hydrogen, halogen Phenoxymethyl substituted with alkyl, alkoxy and thioalkoxy, hydrogen, halogen, thiophenoxymethyl pyridinethiomethyl, pyrimidine thiomethyl and parazolthiomethyl. The 5-fluoromethyl-1, 2, 4-oxadiazole derivatives according to claim 1, wherein R is hydrogen, halogen, nitro substituted phenyl. The 5-fluoromethyl-1, 2, 4-oxadiazole derivative according to claim 1, wherein R is phenylmethyl substituted with hydrogen, halogen, nitro, alkoxy. The 5-fluoromethyl-1, 2, 4-oxadiazole derivative according to claim 1, wherein R is hydrogen, halogen, alkyl group, alkoxy, thioalkoxy substituted phenoxymethyl or thiophenoxymethyl. A compound according to claim 1 or 2, wherein the 1, 2, 4-oxadiazole derivative is 3- (2'-chlorophenyl) -5-fluoromethyl-1, 2, 4-oxadiazole. The compound according to claim 1 or 3, wherein the 1, 2, 4-oxadiazole derivative is 3- (4'-bromophenyl) methyl-5-fluoromethyl-1, 2, 4-oxadiazole. The compound of claim 1 or 4, wherein the 1, 2, 4-oxadiazole derivative is 3- (4'-chlorophenoxy) methyl-5-fluoromethyl-1, 2, 4-oxadiazole. The compound according to claim 1 or 4, wherein the 1, 2, 4-oxadiazole derivative is 3- (2'-methoxyphenoxy) methyl-5-fluoromethyl-1, 2, 4-oxadiazole . 5. The compound of claim 1, wherein the 1, 2, 4-oxadiazole derivative is 3- (3′-trifluoromethylphenoxy) methyl-5-fluoromethyl-1, 2, 4-oxadia Bovine compound. A pesticide containing 1, 2, 4-oxadiazole derivatives substituted with 5-fluoromethyl of the general formula (I) as an active ingredient.

Wherein R is alkoxymethyl, lower alkylaminocarbonylthiomethyl, alkoxyphosphonylthiomethyl, hydrogen, halogen, phenylcarbonyl oxymethyl substituted with alkyl group, hydrogen, halogen, nitro substituted phenyl, hydrogen, halogen, Nitro, alkoxy substituted phenylmethyl, hydrogen, halogen, alkyl group, alkoxy, thioalkoxy substituted phenoxymethyl, hydrogen, halogen, substituted alkyl group thiophenoxymethyl, pyridinethiomethyl, pyrimidine thiomethyl, Pyrazole thiomethyl.