KR900002055B1 - Pyrazole derivatives having pysiological activity and the preparing method thereof - Google Patents

Abstract

R1=arylsulfon, arylsulfide, alkylsulfon, alkylsulfide alkoxycarbonyl, dialkylphosphono; R2=H, lower alkyl, halogen-, nitro-, lower alkyl-substd. phenyl; R3= lower alkyl; R4=alkoxy, halogen-, nitro-substd. phenoxy, thiophenoxy, lower alkylthio; X=O,S) are prepd. Thus 1g (3.7m mol) 1methoxycarbonyl-1- phenylsulfonyl-2-(N,N-dimethyl amino) ethene in ethanol is cooled. 0.224ml (4.4 m mol) methylhydrizine is dropadded to the mixt. The reaction product is stirred for 9 hr followed by removing solvent to give I (R1=II, R2=H).

Description

Physiologically active pyrazole derivatives and preparation method thereof

The present invention relates to novel pyrazole derivatives of the general formula (I) which are useful as insecticides and methods for their preparation.

아릴설폰기, 일반식

의 아릴 설파이드기, 일반식

의 알킬설폰기, R⁵-S-의 알킬 설파이드기, 일반식

의 알콕시 카르보닐기, 일반식

의 디알킬 포스포노기, R²는 수소, 저급알킬기, 할로겐원자 혹은 니트로 치환기 혹은 저급알칼리로 치환되어 있어도 되는 페닐기, R³는 저급알킬기, R⁴는 일반식 -OR⁸의 알콕시기, 하나 또는 그 이상의 할로겐 또는 니트로 치환기를 임의로 갖는 페녹시기 및 티오페녹시기, 저급알킬티오기, R⁵, R⁶, R⁷및 R⁸는 저급알킬기, X는 산소원자 또는 유황원자.Wherein R ₁ is a general formula

Aryl sulfone group, general formula

Aryl sulfide group, general formula

Alkyl sulfone group, R ⁵ -S- alkyl sulfide group, general formula

Alkoxy carbonyl group, general formula

A dialkyl phosphono group, R ² is hydrogen, a lower alkyl group, a halogen atom or a phenyl group which may be substituted with a nitro substituent or a lower alkali, R ³ is a lower alkyl group, R ⁴ is an alkoxy group of the formula -OR ⁸ , or Phenoxy and thiophenoxy groups, lower alkylthio groups, R ⁵ , R ⁶ , R ⁷ and R ⁸ are lower alkyl groups, X is an oxygen atom or a sulfur atom, optionally having more halogen or nitro substituents.

Korean Patent Publication No. 84-255 describes pyrazole type phosphate esters.

However, this document does not mention the compounds of the present invention.

It is therefore an object of the present invention to provide pyrazole derivatives having novel physiological activity.

Still another object of the present invention is to provide a method for preparing a pyrazole derivative having a novel physiological activity.

In the general formula (1), the halogen atom in the substituted phenyl group represented by R ¹ and the halogen atom represented by R ² and R ⁴ are a pullor atom, a chlorine atom or a bromine atom. The lower alkyl group represented by R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , or R ⁸ means a linear or branched alkyl group having 1 to 4 carbon atoms, which is methyl, ethyl, n-propyl, isopropyl, n -Butyl, isobutyl, sec-butyl group, etc. are mentioned. Especially good among them are methyl or ethyl groups. When R ⁴ represents an alkoxy group, a straight or branched chain alkoxy group having 1 to 4 carbon atoms (for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, t-butoxy group) is suitable, but more particularly methoxy or ethoxy group. Examples of the lower alkylthio group represented by R ⁴ include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio group and the like, and in particular, n-propylthio. Group is preferred.

When the compound of the present invention is further characterized and described,

First: R ¹ is (R ⁷ O) ₂ P-, R ⁷ is methyl or ethyl, R ² is methyl, R ³ is methyl or ethyl, R ⁴ is alkoxy, alkylthio, thiophenoxy, O- The chloro phenoxy group and the compound of General formula (1) which X represents oxygen or a sulfur atom are mentioned.

Second: general in which R ¹ is an aryl sulfone group, R ² is methyl group, R ³ is methyl group or ethyl group, R ² is alkoxy group, alkylthio group, thiophenoxy group, O-chlorophenoxy group, X is oxygen or sulfur atom Compound of formula (1).

Third: R ¹ is alkylthio group, R ² is methyl group, R ³ is methyl group or ethyl group, R ⁴ is alkoxy group, alkylthio group, thiophenoxy group, O-chlorophenoxy group, X is oxygen or sulfur atom Compound of general formula (1).

Fourth: R ¹ is an alkoxycarbonyl group, R ² is a methyl group, R ³ is a methyl group or an ethyl group, R ⁴ is an alkoxy group, an alkylthio group, thiophenoxy group, O-chlorophenoxy group, X is an oxygen or sulfur atom The compound of General formula (1) is mentioned.

Specific examples of the compounds according to the invention are those listed in Table 1.

TABLE 1a

TABLE 1b

TABLE 1c

TABLE 1d

TABLE 1e

TABLE 1f

Table 1g

Table 1h

TABLE 1i

The compound of the present invention can be conveniently prepared from pyrazole (2), which is a novel compound. For example, general formula (2)

Wherein R ¹ and R ² are the same as described above. The compound represented by General Formula (3)

In the formula, Hal represents a halogen atom, and R ³ and R ⁴ are the same as those described above. It is preferable to perform reaction of esterification in presence of an acid binder. Suitable acid binders include tertiary amines or hydroxides, oxides, carbonates, bicarbonates, and alkali metal alcoholates of alkali and alkaline earth metals.

As the salt of the 3-hydroxypyrazole compound of the general formula (2), a corresponding alkali metal salt is suitable, and sodium salt, potassium salt and the like are preferable. It is preferable that reaction is generally performed in a suitable inert solvent. The reaction temperature may be selected from -20 to 150 ℃ the temperature at which the reaction proceeds, generally 0 ° -100 ℃. The reaction is completed in 1 hour-6 hours, and the end can be confirmed by thin layer chromatography or the like. After completion of the reaction, the target product can be obtained from the reaction mixture by various means. For example, the reaction solution is filtered and then the solvent is removed to obtain the compound of the present invention. If desired, it may be purified again by means such as distillation, recrystallization, column chromatography, or the like.

The pyrazole (2) used when producing the compound of the present invention by the above method is a novel compound, which can be produced as follows.

Wherein R ¹ , R ² are as defined above and R ⁹ is a lower alkyl group.

It is another object of the present invention to provide a process for the preparation of the novel compound of formula (2) for use as a starting material.

The reaction for making compound (5) from compound (4) can be carried out in a suitable inert solvent or can be carried out without using a solvent. The reaction temperature can be selected from the temperature of the reaction proceeds in the range of -20 ° -50 ℃, 0 ° -100 ℃ is generally suitable. The reaction time is completed at 0.5-8 hours. The reaction for obtaining the desired pyrazole (2) by reacting the compound (5) with a substituted hydrazine is preferably carried out in the presence of a suitable solvent, particularly preferably ethanol. The reaction temperature is not limited but, for convenience, is reacted within a temperature range between -20 ° C and the reflux temperature of the solvent. The reaction time is completed at 2-8 hours. Upon completion of the reaction, the desired compound is separated from the reaction mixture in various ways and, if necessary, purified by conventional methods such as distillation, recrystallization or chromatography.

Particular examples of pyrazole (2) according to the invention are those listed in Table 2.

TABLE 2

Compound (1) of the present invention exhibits excellent control effects against hygienic pests, plant parasitic insects, mites and mites. Test of pesticidal and acaricide activity for several representatively selected compounds is detailed in Experimental Example 15.

The present invention will be described in detail by the following examples, but the present invention is not limited to these examples.

Example 1

3-hydroxy-1-methyl-4-phenylsulfonyl pyrazole (Compound No. 170):

1 g (3.7 mmol) of 1-methoxycarbonyl-1-phenylsulfonyl-2- (N, N-dimethylamino) ethene is added to ethanol and cooled to 0 ° C.

Methyl hydrazine (0.24 ml, 4.4 mmol) is added dropwise here.

The reaction mixture is stirred at 0 ° C. for 1 hour, at room temperature for 4 hours, and under reflux for 4 hours. After the completion of the reaction, the solvent was removed under vacuum, and then vacuum distilled to obtain a red liquid. This was recrystallized from ethanol to give 0.63 g of pyrazole as a solid. Melting point: 193-194 ° C.

¹ H NMR (DMSO-d ₆ ): 3.7 (s, 3H), 7.2-7.85 (m, 6H), 9.8 (s, 1H).

MS (70 eV) 238 (M < ^{+ &} gt ^; ).

In the same manner as described above, Compound Nos. 169 and 171 were obtained using hydrazine and phenylhydrazine instead of methyl hydrazine.

Example 2

3-hydroxy-1-methyl-4-phenylthiopyrazole (Compound No. 173):

1 g (4.2 mmol) of 1-methoxycarbonyl-1-phenylthio-2- (N, N-dimethylamino) ethene is added to ethanol and cooled to 0 ° C. To this was added methylhydrazine (0.27 ml, 5.0 mmol) dropwise. The reaction mixture is stirred at 0 ° C. for 1 hour, at room temperature for 2 hours and under reflux for 5 hours. After the completion of the reaction, the solvent was removed in vacuo and then recrystallized from ethanol to obtain 0.65 g of pyrazole.

¹ H NMR (DMSO-d ₆ ): 3.65 (s, 1H), 7.1-7.55 (m, 6H), 9.5 (s, 1H).

MS (70 eV) 206 (M ^< ^{+ &} gt ^; ).

Compound Nos. 172 and 174 were prepared using hydrazine and phenylhydrazine instead of methylhydrazine in the same manner as described above.

Example 3

3-hydroxy-1-methyl-4-methylsulfonyl pyrazole (Compound No. 176):

1-Ethoxycarbonyl-1-methylsulfonyl-2- (N, N-dimethylamino) ethene (1 g, 4.5 mmol) was added to ethanol and cooled to 0 ° C. To this was added methylhydrazine (0.26 ml, 4.9 mmol) dropwise. The reaction mixture is stirred at 0 ° C. for 1 hour, at room temperature for 2 hours and under reflux for 4 hours. After completion of the reaction, the solvent was removed in vacuo and column chromatography on silica gel with a mixture of methanol and ethyl acetate (1: 4) afforded the desired compound as a solid (0.55 g).

¹ H NMR (DMSO-d ₆ ): 2.95 (s, 3H), 3.3 (s, 3H), 7.1 (s, 1H), 10.0 (s, 1H).

MS (70 eV) 176 (M ^< ^{+ &} gt ^; ).

Compound No. 175,177 was prepared using hydrazine and phenylhydrazine instead of methylhydrazine in the same manner as described above.

Example 4

3-hydroxy-1-methyl-4-methylthiopyrazole (Compound No. 179):

1-ethoxycarbonyl-1-methylthio-2- (N, N-dimethylamino) ethene (1 g, 5.3 mmol) in ethanol (10 ml) is cooled to 0 ° C. To this is added methylhydrazine (0.3 ml, 5.8 mmol) dropwise. The reaction mixture was stirred at 0 ° C. for 1 hour at room temperature under reflux for 4 hours for 2 hours. The solvent was removed in vacuo and column chromatography was performed on silica gel with a mixed solution of methanol and ethyl acetate (1:49) to give pyrazole as a white solid (0.6 g).

¹ H NMR (CDCl ₃ ): δ 2.1 (S, 3H), 3.5 (s, 3H), 7.3 (s, 1H), 10.5 (s, 1H).

MS (70 eV) 144 (M ^< ^{+ &} gt ^; ).

Compound number 178,180 was prepared using hydrazine and phenylhydrazine instead of methylhydrazine in the same manner as described above.

Example 5

3-hydroxy-1-methyl-4-ethoxycarbonylpyrazole (Compound No. 182):

1, 1-diethoxycarbonyl-2- (N, N-dimethylamino) ethene (1 g, 4.6 mmol) is placed in ethanol (10 ml) and cooled to 0 ° C. To this was added methylhydrazine (0.27 ml, 5.1 mmol) dropwise. The reaction mixture was stirred at 0 ° C. for 1 hour, at room temperature for 3 hours, and under reflux for 1 hour. After completion of the reaction, the solvent was removed in vacuo and recrystallized from ethanol to give a white solid (0.65 g).

¹ H NMR (CDCl ₃ ): δ 1.3 (t, 3H), 3.65 (s, 3H), 4.15 (q, 2H), 7.5 (s, 1H), 8.5 (s, 1H).

MS (70 eV) 170 (M ⁺ ).

Compound number 181,183 was prepared using hydrazine and phenylhydrazine instead of methylhydrazine in the same manner as described above.

Example 6

3-hydroxy-1-methyl-4-diethylphosphonopyrazole (Compound No. 185):

1-methoxycarbonyl-1-diethylphosphono-2- (N, N-dimethylamino) ethene (1 g, 3.8 mmol) is placed in ethanol (10 ml) and cooled to 0 ° C. To this was added methylhydrazine (0.33 g, 3.8 mmol) dropwise. The reaction mixture is stirred at 0 ° C. for 1 hour, at room temperature for 4 hours and under reflux for 2 hours. After the completion of the reaction, the solvent was removed in vacuo and distilled under reduced pressure to yield a colorless liquid (0.78 g).

¹ H NMR (CDCl ₃ ): 1.3 (t, 6H), 3.6 (s, 3H), 4.0 (q, 4H), 7.3 (s, 1H), 9.7 (s, 1H).

MS (70 eV) 234 (M ^< ^{+ &} gt ^; ).

Compound number 184,186 was prepared using hydrazine and phenylhydrazine instead of methylhydrazine in the same manner as described above.

Example 7

3-hydroxy-1-methyl-4-dimethylphosphonoparasol (Compound No. 188):

1-methoxycarbonyl-1-dimethylphosphono-2- (N, N-dimethylamino) eden (1 g, 4.2 mmol) is placed in ethanol (10 ml) and cooled to 0 ° C. To this was added methylhydrazine (0.25 ml, 4.6 mmol) dropwise. The reaction mixture is stirred at 0 ° C. for 1 hour, at room temperature for 5 hours and under reflux for 2 hours. After the completion of the reaction, the solvent was removed in vacuo and distilled under reduced pressure to obtain a colorless liquid (0.56 g).

¹ H NMR (CDCl ₃ ): 3.5 (s, 3H), 3.55 (s, 3H), 3.7 (s, 3H), 7.2 (s, 1H), 9.55 (s, 1H).

MS (70 eV) 206 (M ^< ^{+ &} gt ^; ).

Compound number 187,189 was prepared using hydrazine and phenylhydrazine instead of methylhydrazine in the same manner as described above.

Example 8

0, 0-diethyl-0- (1-methyl-4-phenylsulfonylpyrazol-3-yl) phosphate ester (Compound No. 10):

3-hydroxy-1-methyl-4-phenylsulfonyl pyrazole (0.5 g, 2.1 mmol) in acetonitrile (10 ml), diethylchlorophosphate (0.3 ml, 2.1 mmol) and potassium carbonate (0.87 g) Was stirred at room temperature for 5 hours. The reaction was filtered, and the solvent was removed in vacuo to give a colorless oil (0.55 g). This oil was purified by column chromatography on silica gel with a mixture of hexane and ethyl acetate (1: 1) as a solvent to give a colorless oil (0.51 g). Nuclear magnetic resonance spectra of the product showed this was the desired compound number (10).

¹ H NMR (CDCl ₃ ): 1.35 (t, 6H), 3.80 (s, 3H), 4.25 (q, 4H), 7.30-8.01 (m, 6H).

MS (70 eV) 374 (M ^< ^{+ &} gt ^; ).

Compound No. 1-24 was prepared using hydrazine and phenyl hydrazine instead of appropriate chlorophosphate methylhydrazine in place of diethyl chlorophosphate in the same manner as above. MS and ¹ H NMR of the representative compounds are as follows.

Compound number 9.

¹ H NMR (CDCl ₃ ): 3.7 (s, 3H), 3.76 (s, 3H), 3.95 (s, 3H), 7.30-8.00 (m, 6H).

MS (70 eV) 346 (M ^< ^{+ &} gt ^; ).

Compound number 14.

¹ H NMR (CDCl ₃ ): 1.36 (t, 6H), 3.82 (s, 3H), 4.30 (q, 4H), 7.35-8.01 (m, 6H).

MS (70 eV) 390 (M ^< ^{+ &} gt ^; ).

Example 9

0, 0-diethyl-0- (1-methyl-4-phenylthiopyrazol-3-yl) phosphate ester

(Compound No. 34):

3-hydroxy-1-methyl-4-phenylthiopyrazole (0.5 g, 2.4 mmol) in acetonitrile (10 ml), diethyl chlorophosphate (0.35 ml, 2.4 mmol) and potassium carbonate (1.0 g, 7.3 Myrimol) was stirred at room temperature for 4 hours. The following operations were carried out in the same manner as in Example 8 to obtain oil (0.6 g).

¹ H NMR (CDCl ₃ ): 1.35 (t, 6H), 3.70 (s, 3H), 4.20 (q, 4H), 7.1-7.60 (m, 6H).

MS (70 eV) 342 (M ^< ^{+ &} gt ^; ).

Compounds 25-48 were prepared using the appropriate chlorophosphate esters in place of diethylchlorophosphate in the same manner as described above.

Example 10

0, 0-diethyl-0- (1-methyl-4-methylsulfonylpyrazol-3-yl) phosphate ester (Compound No. 58):

3-hydroxy-1-methyl-4-methylsulfonylpyrazole (0.5 g, 2.8 mmol), diethylchlorophosphate (0.41 ml, 2.8 mmol) and triethylamine (0.40 ml) in methylene chloride (5 ml) , 2.8 mmol) was stirred at room temperature for 5 hours. After completion of the reaction, the reaction was filtered, the solvent was removed in vacuo, and the residue was purified by column chromatography on silica gel using a mixture of hexane and ethyl acetate (1: 1) as a solvent to give an oil (0.74 g). Got it.

¹ H NMR (CDCl ₃ ): δ 1.35 (t, 6H), 2.95 (s, 3H), 3.35 (s, 3H), 4.20 (q, 4H), 7.1 (s, 1H).

MS (70 eV) 312 (M < ^{+ &} gt ^; ).

In the same manner as described above, compounds Nos. 49-72 were prepared using the appropriate chlorophosphate esters in place of diethyl chlorophosphate.

Example 11

0, 0-diethyl-0- (1-methyl-4-methylthiopyrazol-3-yl) thiophosphate ester (Compound No. 86).

3-hydroxy-1-methyl-4-methylthiopyrazole (0.5 g, 3.5 mmol) in methylene chloride (5 ml), diethyl chlorothiophosphate (0.55 ml, 3.5 mmol) and triethylamine (0.48 ml , 1.35 mmol) was stirred at room temperature for 4 hours. The following operations were carried out in the same manner as in Example 10, to obtain a colorless oil (0.87 g).

¹ H NMR (CDCl ₃ ): δ 1.37 (t, 6H), 2.30 (s, 3H), 3.62 (s, 3H), 4.28 (q, 4H), 7.82 (s, 1H).

MS (70 eV) 296 (M ^< ^{+ &} gt ^; ).

In the same manner as described above, compounds Nos. 73-96 were prepared using appropriate chlorophosphate esters instead of diethyl chlorothiophosphate, and NMR and MS of the representative compounds are as follows.

Compound number 82.

¹ H NMR (CDCl ₃ ): δ 1.35 (t, 6H), 2.25 (s, 3H), 3.7 (s, 3H), 4.25 (q, 4H), 7.25 (s, 1H).

MS (70 eV) 280 (M ⁺ ).

Compound number 85.

¹ H NMR (CDCl ₃ ): δ 2.25 (s, 3H), 3.7 (s, 3H), 3.8 (s, 3H), 4.0 (s, 3H), 7.35 (s, 1H).

MS (70 eV) 268 (M ^< ^{+ &} gt ^; ).

Example 12

0, 0-diethyl-0- (1-methyl-4-ethoxycarbonylpyrazol-3-yl) phosphate ester (Compound No. 106).

3-hydroxy-1-methyl-4-ethoxycarbonylpyrazole (0.5 g, 2.9 mmol) in methylene chloride (5 ml), diethylchlorophosphate (0.43 ml, 2.9 mmol) and triethylamine (0.41 ml, 2.9 mmol) was stirred at room temperature for 5 hours. The following operation was performed like Example 10 and the colorless oil (0.8g) was obtained.

¹ H NMR (CDCl ₃ ): δ 1.40 (t, 9H), 3.75 (s, 3H), 4.2 (q, 6H), 7.6 (s, 1H).

MS (70 eV) 306 (M ^< ^{+ &} gt ^; ).

In the same manner as described above, compounds No. 97-120 were prepared using appropriate chlorophosphate esters instead of diethylchlorophosphate, and NMR and MS of the representative compounds are as follows.

Compound number 110:

¹ H NMR (CDCl ₃ ): δ 1.30 (t, 9H), 3.75 (s, 3H), 4.10 (m, 6H), 7.40 (s, 1H).

MS (70 eV) 322 (M ^< ^{+ &} gt ^; ).

Example 13

0, 0-diethyl-0- (1-methyl-4-diethylphosphonopyrazol-3-yl) thiophosphate ester (Compound No. 134).

3-hydroxy-1-methyl-4-diethylphosphonopyrazole (0.5 g, 2.1 mmol) in methylene chloride (5 ml), diethylchlorothiophosphate (0.34 ml, 2.1 mmol) and triethylamine ( 0.30 ml, 2.1 mmol) was stirred at room temperature for 7 hours. The following operation was performed like Example 10 and the colorless oil (0.67g) was obtained.

¹ H NMR (CDCl ₃ ): 1.3 (m, 12H), 3.7 (s, 3H), 4.0 (m, 8H), 7.3 (s, 1H).

MS (70 eV) 386 (M ^< ^{+ &} gt ^; ).

In the same manner as described above, compounds Nos. 121-144 were prepared using chlorophosphate esters instead of diethylchloro thiophosphate, and NMR and MS of the representative compounds are as follows. Compound number 122.

¹ H NMR (CDCl ₃ ): δ 1.3 (m, 12H), 4.0 (m, 8H), 7.6 (s, 1H), 12.0 (s, 1H).

MS (70 eV) 356 (M ^< ^{+ &} gt ^; ).

Compound number 129.

¹ H NMR (CDCl ₃ ): δ 1.3 (t, 6H), 3.5 (d, 6H), 3.9 (s, 3H), 4.0 (q, 4H), 7.3 (s, 1H).

MS (70 eV) 342 (M ^< ^{+ &} gt ^; ).

Compound number 130.

¹ H NMR (CDCl ₃ ): δ 1.3 (m, 12H), 4.1 (m, 11H), 7.3 (s, 1H).

MS (70 eV) 370 (M ^< ^{+ &} gt ^; ).

Example 14

0, 0-diethyl-0- (1-methyl-4-dimethylphosphonopyrazol-3-yl) phosphate ester (Compound No. 154):

3-hydroxy-1-methyl-4-dimethylphosphonopyrazole (0.5 g, 2.4 mmol) in methylene chloride (5 ml), diethylchlorophosphate (0.35 ml, 2.4 mmol) and triethylamine (0.34 ml) , 2.4 mmol) was stirred at room temperature for 6 hours. The following operation was carried out similarly to Example 10, and oil (0.66g) was obtained.

¹ H NMR (CDCl ₃ ): δ 1.4 (t, 6H), 3.6 (s, 3H), 3.8 (s, 6H), 4.2 (q, 4H), 7.3 (s, 1H).

MS (70 eV) 342 (M ^< ^{+ &} gt ^; ).

In the same manner as described above, compound Nos. 145-168 were prepared using an appropriate chlorophosphate ester in place of diethyl chlorophosphate.

Experimental Example 1

Representative pyrazole compounds prepared according to the methods of the invention are evaluated by the following test methods in terms of pesticidal and acaricidal activity. To prepare the test chemicals, 50 milligrams of the test compound is completely dissolved in 5 milliliters of acetone, and then mixed with 45 milliliters of a Triton X-100 100 ppm aqueous solution, which is a surfactant, to prepare a test solution having a concentration of 1000 ppm. The test process is as follows.

end. Brown planthopper

The pest (BPH) (Nilaparvata lugens stal) is a sensitized strain that was raised indoors without insecticides, and the larvae of a certain age so that the final adult density per acrylic cage (26 cm, 29 cm, 20 cm in height) is approximately 500 Breeding indoors using Dongjin rice in a greenhouse (temperature 27 ± 1 ℃), relative humidity 50 ± 5%, light conditions 16 persons 8 cancer). Insecticidal testing reveals adult females 4 days after fable.

Six seedlings (breed; Dongjin), 5-7 cm tall, are rolled with cotton wool, inserted into a test tube (3 cm in diameter, 15 cm in height), and 20 adult insects are inoculated. A nozzle of a micro atomizer (a single injection amount of 0.0254 ± 0.0005 ml) is placed at the center of the inlet of the test tube, and the 1000 ppm suspension liquid is sprayed twice. The control treated with acetone-surfactant-heavy water solution containing no test agent. Each treatment is carried out in three repetitions. After treatment, the mortality rate was examined after 24 hours and 48 hours while being kept in a constant temperature room (temperature 25 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people 8 cancer). Those who did not show reflexes when stimulated with saliva are considered dead individuals.

I. Green Peach aphid

The insect pest (GPA) (Myzus persicae sulzer) is a breeding system without insecticides for 2 years indoors in a constant temperature room (temperature 21 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people 8 cancers); Indoor breeding using NC-82). Insecticide tests are to be published with neglected class.

The test compound was immersed in 50 milliliters of the 1000 ppm test solution as described in the preparation of the above-mentioned chemical solution (variety; NC-82) cut into a 9 cm diameter toy for 30 seconds, then passed through for 30 minutes, and placed in a 9 cm Petri dish. The control was immersed in acetone-surfactant-distilled water solution. Each treatment is carried out in three repetitions. 20 insects were inoculated into each treated tobacco leaf and stored in yellow-green room (temperature 25 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people, 8 cancers). Investigate. Those who do not show reflexes when stimulated with a thin brush tip are considered dead.

All. Soybean aphid

The pest (SA) (Aphis glycines matsumura) is a system that was raised in a room without insecticides for two years in the room, soybeans in a constant temperature room (temperature 21 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people, 8 cancers) Breed indoors as host plants. Insecticidal tests are also disclosed with nymphs.

The test compound was soaked in 50 milliliters of the 1000 ppm test chemical solution as described in the above-mentioned pharmaceutical preparation method for 30 seconds, and then air-dried for 30 seconds, and then fixed in polystyrene (6 cm in diameter and 7.5 cm in height). The control was deposited in acetone-surfactant-distilled water solution. Each treatment is carried out in three repetitions. 20 insects were inoculated into each treated soybean leaf and stored in a constant temperature room (temperature 25 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people, 8 cancers) and examined for mortality after 24 hours and 48 hours. do. When irritated with a thin brush tip, it does not show reflex action.

la. Diamond-back moth

The insect pest (DBH) (Plutella xylostella linnaeus) was bred using the cabbage at the temperature (27 ± 1 ℃, relative humidity 50 ± 5%, 16 light conditions, 8 cancers) without any pesticide selection. The average density per breeding box is around 500, and three larvae should be published for pesticide testing.

Cut the cabbage leaves into 9cm diameter circles, soak them in 1000ppm test chemicals for 30 seconds and air dry for 30 minutes. The control treated with acetone-surfactant-distilled water solution that did not contain the test compound. The treated leaves are placed in a 9 cm diameter Petri dish and inoculated with 10 3 larvae. Each treatment is repeated three times. Petri dishes are covered with a lid and kept at a constant temperature (temperature 25 ± 1 ℃, relative humidity 50 ± 5%, light conditions of 16 people, 8 cancers) and examined for mortality after 24 hours and 48 hours. . Anything that does not show reflexes when touched with a thin brush tip is considered dead.

hemp. Bean Bug

The pests (Riptortus Clartitus Thunberg) were collected outdoors, and cultivated with no pesticides in a constant temperature room (temperature 25 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people 8 cancer) for more than 1 year to the construction layer. use. Insecticidal test was carried out by immersing 3 minutes of soybean seedlings (5-7 days after sowing, roots 4-5cm) germinated in the exclusion of water-containing vermiculite for 30 seconds and rubella, and then ø6 × 3.5cm transparent Place in a polyethylene container and inoculate 10 layers of 3rd material. On the other hand, the control group is treated with acetone-surfactant-distilled water solution that does not contain the disclosed drug. Repeated treatment three times for the test group and the control group, and then covered with a lid of the container 24 hours, 48 hours while storing in a constant temperature room (temperature 25 ° ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people 8 cancer) Examine mortality later. When irritated with fine needles, no reflexes are caused by death.

bar. Two-spotted spider mite

The insect pest (TSSM) (Tetranychus urticae koch) is a breeding indoors using gangnambean leaves in a pesticide-sensitive system in a constant temperature room (temperature 23 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people 8 cancer). Insecticide tests reveal the adult.

Agar solution (0.5% agar content) is poured into the case to a depth of about 1cm, the Gangnam bean leaves are fixed on it, 40 adult seeds are inoculated, and 3 milliliters of the 1000 ppm test chemical solution is sprayed using a micro sprayer. The control is sparged with an acetone-surfactant-distilled water solution that does not contain the test compound. Each treatment is repeated three times. After treatment, the mortality rate was examined by microscopic observation 24 hours and 48 hours in a constant temperature room (temperature 25 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people, 8 cancers). Moving when stimulating is considered alive.

The test results obtained by the above method are shown in Table 3 as the mortality rate and the mortality rate was calculated by the following equation.

TABLE 3

As can be seen in Table 1, the novel compounds of the present invention have excellent physiological activity compared to the compounds listed in Patent Publication No. 84-255.

Compound (1) of the present invention is effective as an insecticide.

The compounds of the present invention may be administered in one or two or more mixtures in a suitable form, such as emulsions, wetting agents, powders, granules, etc., by mixing with a suitable carrier and / or diluent.

The content rate of the active ingredient of this invention differs according to the purpose of use.

For example, an emulsion, a hydrating agent, etc. is preferable 10-90% (weight), and powder, etc., 0.1-10% (weight) is preferable, but a change of this quantity is possible according to a use purpose.

Examples of the carrier for use in the composition of the present invention include liquids such as water, alcohols (monohydric alcohols such as methanol, dihydric alcohols such as ethylene glycol and trihydric alcohols such as glycerin), cantons (acetone, methyl ethyl ketone, etc.), Ethers (dioxane, tetrahydrofuran, cellosolve, etc.), aliphatic hydrocarbons (gasoline, kerosene, kerosene, etc.), aromatic hydrocarbons (benzene, toluene, xylene, solvent, naphtha, etc.), halogenated hydrocarbons ( Chloroform, carbon tetrachloride, etc.), acid amides (dimethylformamide, etc.), esters (ethyl acetate, butyl acetate, fatty acid glycerin esters, etc.), and nitriles (acetonitrile, etc.), and these may be used alone or in combination. It can be used as a mixture.

As the solid carrier, mineral particles (kaolin, clay, bentonite, acid clay, talc, diatomaceous earth, silica, sand, etc.), plant powder (wood powder, etc.), and other mineral particles can be used.

An emulsifier, an electrodeposition agent, a dispersing agent, a true lubricant etc. can be used for the composition of this invention. For example, nonionic, anionic or cationic surfactants such as fatty acid soda, polyoxyalkyl esters, alkylsulfonates, polyethylene glycol ethers, and the like can be used.

The composition of the present invention may also be used in combination with other kinds of agrochemically active ingredients, such as conflicting agents, herbicides, plant hormones, fungicides and the like.

In addition, the composition of the present invention may be used by mixing a fertilizer or the like (% in the following composition examples are all weight%).

Composition Example 1 (Emulsion)

Compound number 170 20%

Xylene 75%

Polyoxyethylene glycol ether 5%

The above ingredients were mixed to prepare an emulsion.

Composition Example 2 (Powder)

Compound number 180 5%

Kaolin 94.6%

Silicone (defoamer) 0.3%

Polyethylene glycol ether 0.1%

The powder was prepared by mixing the above components.

Composition Example 3 (Hydrating)

Compound number 188 30%

Lignin sulfoic acid soda 5%

Polyoxyethylene glycol ether 5%

Bentonite 60%

The above ingredients were mixed to prepare a hydrating agent.

Composition Example 4 (granular)

Compound number 176 10%

Lignin sulfonic acid soda 5%

Bentonite 85%

Water was added to the ingredients to knead and then granulated to prepare granules.

Claims (5)

Compound represented by the following general formula (1)

Wherein R ¹ is a general formula

Aryl sulfone group, general formula

Aryl sulfide group, general formula

Alkyl sulfone group, R ⁵ -S- alkyl sulfide group, general formula

Alkoxy carbonyl group, general formula

A dialkyl phosphono group, R ² is hydrogen, a lower alkyl group, a halogen atom or a phenyl group which may be substituted with a nitro substituent or a lower alkyl group, R ³ is a lower alkyl group, R ⁴ is an alkoxy group of the formula -OR ⁸ , or Phenoxy and thiophenoxy groups, lower alkylthio groups, R ⁵ , R ⁶ , R ⁷ and R ⁸ are lower alkyl groups, X is an oxygen atom or a sulfur atom, optionally having more halogen or nitro substituents. The compound represented by following General formula (2).

(Wherein R ¹ and R ² are as defined above). Or the compound represented by the following general formula (3)

Wherein R ³ , R ⁴ and X are as defined above and Hal is halogen. A method of preparing the following compound of formula (1):

(Wherein R ¹ , R ² , R ³ , R ⁴ and X are as described above). The compound represented by general formula (2).

(Wherein R ¹ and R ² are as defined above). Compound represented by the following general formula (5)

Wherein R ¹ is as defined above and R ⁹ is a lower alkyl group. The compound represented by the following general formula (6). R ² NHNH ₂ (6) (In which R <^2> is as above-mentioned.) The method of manufacturing the compound represented by following General formula (2) by making it react.

(Wherein R ¹ and R ² are as defined above). Compound represented by the following general formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and X are as described above.) A composition for agrochemicals containing a carrier, a diluent, a surfactant, etc. which are commonly used as an agrochemical.