KR20010036702A - A insecticidal composition containing catethcol hydrazone derivatives - Google Patents

Abstract

PURPOSE: An insecticidal composition comprising an effective amount of novel cathecol hydrazone derivatives, pharmaceutically acceptable salts and carriers generally used in the field of agricultural chemicals is provided, which exhibits excellent insecticidal activity. CONSTITUTION: This composition is characterized in that it contains an effective amount of a compound of formula(1) to control insects, pharmaceutically acceptable salts and carriers generally used in the field of agricultural chemicals. In formula, R1 is C1-7 alkyl or C3-7 cycloalkyl; R2 is -H, -OH, -C1 to 5 alkyl or -CH2CH2C(=O)NH2; R3 or R4 are each independently i)-H, ii)C1-7 alkyl, iii)-C(=X)-R5, iv)substituted 2-, 3- or 4- pyridyl or phenyl or v)a ring compound directly connected to C3-4 containing O, S or N; X is O, S or N-R5; R5 is i)-C1-7 alkyl, ii)-NHR6 or iii)substituted 2-, 3- or 4- pyridyl, pyrimidyl or phenyl; and R6 is -H, -OH, -C1-5 alkoxy, -C1-5 alkyl, pyridyl or phenyl.

Description

A pesticidal composition containing catethcol hydrazone derivatives

The present invention relates to pesticides. More particularly, the present invention is characterized in that it contains an effective amount of a catechol hydrazone derivative compound of formula (I) or a pharmaceutically acceptable salt thereof and a carrier commonly used in the pesticide field in an amount effective to eliminate pests. A pesticide composition comprising:

(I)

Wherein R ¹ is C ₁ -C ₇ alkyl or C ₃ -C ₇ cycloalkyl, R ² is —H, —OH, —C ₁ -C ₅ alkyl or —CH ₂ CH ₂ C (═O) NH ₂ and R ³ or R ⁴ are each independently i) -H, ii) C ₁ -C ₇ alkyl, iii) -C (= X) -R ⁵ , iii) halogen, C ₁ -C ₆ alkoxy, nitrile , 2-, 3- or 4-pyridyl, pyrimidyl or phenyl group optionally substituted with one or two of trifluoromethyl, C ₁ -C ₆ alkyl and carboxylic acid groups, or iii) oxygen, sulfur or nitrogen A cyclic compound connected directly to C ₃ -C ₄ containing X, X is O, S or NR ⁶ , R ⁵ is i) -C ₁ -C ₇ alkyl, ii) -NHR ⁶ or iii) halogen, nitrile, Is a 2-, 3- or 4-pyridyl, pyrimidyl or phenyl group with optionally substituted trifluoromethyl, (C ₁ -C ₆ ) alkyl or carboxylic acid groups, and R ⁶ is —H, —OH, — ( C ₁ -C ₅ ) alkoxy, — (C ₁ -C ₅ ) alkyl, pyridyl or phenyl group.

It is an object of the present invention to provide novel insecticides which are excellent in insecticidal activity and very useful by using compounds which are structurally completely different from compounds showing conventional pesticidal activity.

The inventors have found that the catechol hydrazone derivative compounds exhibit excellent pesticidal activity.

The present invention relates to an insecticide composition characterized in that it contains an amount of a catechol hydrazone derivative compound of formula (I) and a pharmaceutically acceptable carrier thereof in an amount effective to remove the pests:

(I)

In the above formula,

R ¹ is C ₁ -C ₇ alkyl or C ₃ -C ₇ cycloalkyl;

R ² is —H, —OH, —C ₁ -C ₅ alkyl or —CH ₂ CH ₂ C (═O) NH ₂ ;

R ³ or R ⁴ are each independently i) -H, ii) C ₁ -C ₇ alkyl, i) -C (= X) -R ⁵ , i) halogen, C ₁ -C ₆ alkoxy, nitrile, trifluor A 2-, 3- or 4-pyridyl, pyrimidyl or phenyl group optionally substituted with one or two of rommethyl, C ₁ -C ₆ alkyl and carboxylic acid groups, or iii) containing oxygen, sulfur or nitrogen Cyclic compounds directly linked to C ₃ -C ₄ ;

X is O, S or NR ⁵ ;

R ⁵ is 2-, 3- optionally substituted from i) -C ₁ -C ₇ alkyl, ii) -NHR ⁶ or iii) halogen, nitrile, trifluoromethyl, C ₁ -C ₆ alkyl and carboxylic acid groups Or 4-pyridyl, pyrimidyl or phenyl group;

R ⁶ is —H, —OH, —C ₁ -C ₅ alkoxy, —C ₁ -C ₅ alkyl, pyridyl or phenyl group.

Compound (I) which is an active ingredient of the present invention may exist in the form of optical isomers or geometric isomers, and the active ingredient of the present invention includes these isomers and mixtures thereof.

Compound of formula (I) as an active ingredient of the present invention is prepared by the following scheme (I).

Scheme I

Some derivatives were synthesized by known methods (J. Med. Chem., 1994, 37, 1696) and hydrazine compounds were synthesized in alcoholic solvents in 60-90% yield using acid catalysts (Tetrahedron. Lett. 1994, 35 , 3711).

The invention is illustrated more specifically in the following examples. However, these examples merely illustrate and illustrate the invention and should not be construed as limiting the invention to these examples.

Reference Example 1

3-cyclopentyloxy-4-methoxybenzaldehyde

Isovanillin (100 g, 0.66 mol), anhydrous potassium carbonate (136.2 g, 0.99 mol),

A suspension of potassium iodide (3 g) and anhydrous dimethylformamide (650 mL) was stirred at 65 ° C., and then cyclopentyl bromide (127.3 g, 0.85 mol) was slowly added dropwise to the suspension for 1 hour, followed by stirring at 65 ° C. for 1 day. After lowering the temperature to room temperature, toluene (2.0L) was added to the mixed solution and diluted, and washed with 1M sodium hydroxide (2x1.5L). The obtained aqueous layer solution was extracted with toluene (0.5 L), and the obtained organic layer was washed with distilled water (2 × 1.5 L). The organic layer was dried and concentrated to give a light brown oily title compound (117 g).

¹ H NMR (CDCl 3, d): 9.84 (s, 1H) 7.42 (m, 2H) 6.95 (d, 1H, J = 9 Hz) 4.87 (m, 1H)

3.93 (s, 3H) 2.1-1.6 (m, 8H)

Example 1.

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde isnicotinichydrazone

0.44 g (2.0 mmol) of the compound of Reference Example 1 was diluted in 30 ml of ethanol, and then a catalytic amount of concentrated sulfuric acid was added thereto, followed by stirring at room temperature for 10 minutes. 0.33 g of isonicotinic hydrazide was added to the reaction solution, followed by stirring at 50 ° C. for 4.0 hours. The residue obtained by concentrating the solvent under reduced pressure was diluted with dichloromethane and washed twice with 50 ml of distilled water. The separated organic layer was dried over anhydrous acetic acid, distilled under reduced pressure to obtain white crystals, and then recrystallized from dichloromethane to give 0.67 g (88.450%) of the title compound as white.

Melting Point: 170 ~ 171 ℃

¹ H NMR (DMSO-d6): 1.60 (2H, m) 1.75 (4H, m) 1.92 (2H, m) 3.81 (3H, s) 4.85 (1H, m) 7.04 (1H, d J = 8.4 Hz) 7.24 (1H, dd, J = 8.4, 1.8 Hz) 7.33 (1H, d J = 1.8 Hz) 7.81 (2H, dd, J = 4.5, 1.6 Hz) 8.39 (1H, s) 8.78 (2H, dd, J = 4.5 , 1.6 Hz) 11.92 (1H, s)

Example 2

(E) -ethyl [(3-cyclopentyloxy-4-methoxyphenyl) methylene] carbazate

After diluting 1.00 g (4.54 mmole) of the compound of Reference Example 1 in 80 ml of ethanol, a catalytic amount of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 10 minutes. 0.73 g of ethyl carbazate was added to the reaction solution, followed by stirring at 50 ° C. for 4.0 hours. The residue obtained by concentrating the solvent under reduced pressure was diluted with dichloromethane and washed twice with 50 ml of distilled water. The separated organic layer was dried over anhydrous acetic acid, distilled under reduced pressure to obtain white crystals, and then recrystallized from dichloromethane to obtain 1.25 g (89.87%) of a white title compound.

Melting Point: 146 ~ 147 ℃

¹ H NMR (DMSO-d6): 1.23 (3H, t, J = 7.1 Hz) 1.58 (2H, m) 1.73 (4H, m) 1.88 (2H, m) 3.77 (3H, s) 4.13 (2H, q, J = 7.1 Hz) 4.80 (1H, m) 6.98 (1H, d J = 8.4 Hz) 7.07 (1H, dd, J = 8.4, 1.9 Hz) 7.20 (1H, d J = 1.9 Hz) 7.93 (1H, s) 10.92 (1 H, s)

Example 3

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde phenylhydrazone

0.50 g (2.27 mmole) of the compound of Reference Example 1 was diluted in 60 ml of ethanol, and then a catalytic amount of concentrated hydrochloric acid was added, followed by stirring at room temperature for 10 minutes. 0.34 ml of phenylhydrazine was added to the reaction solution, followed by stirring at 50 ° C. for 10 hours. The resulting precipitate was filtered and washed with 20 ml of ethanol to obtain 0.63 g (89.41%) of the title compound as white.

Melting Point: 138 ~ 140 ℃

¹ H NMR (DMSO-d6): 1.60 (2H, m) 1.75 (4H, m) 1.92 (2H, m) 3.77 (3H, s) 4.85 (1H, m)

6.72 (1H, m) 6.95 (1H, d J = 8.2 Hz) 7.03 (2H, d, J = 7.6 Hz) 7.09 (1H, dd, J = 8.2, 1.8 Hz) 7.20 (2H, t) 7.26 (1H, d J = 1.8 Hz) 7.78 (1H, s) 10.12 (1H, s)

Example 4

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde acetic hydrazone

0.50 g (2.27 mmole) of the compound of Reference Example 1 was diluted in 60 ml of ethanol, and then a catalytic amount of concentrated hydrochloric acid was added, followed by stirring at room temperature for 10 minutes. 0.26 g of acetic hydrazide was added to the reaction solution, followed by stirring at 25 ° C. for 10 hours. The residue obtained by concentrating the solvent under reduced pressure was diluted with dichloromethane and washed twice with 50 ml of distilled water. The separated organic layer was dried over anhydrous acetic acid, distilled under reduced pressure to obtain white crystals, and then recrystallized from dichloromethane to obtain 0.59 g (94.06%) of the title compound as white.

Melting Point: 155 ~ 156 ℃

¹ H NMR (DMSO-d6): 1.58 (2H, m) 1.71 (4H, m) 1.88 (2H, m) 2.18 (3H, s) 3.78 (3H, s)

4.81 (1H, m) 6.99 (1H, d J = 8.4 Hz) 7.14 (1H, dd, J = 8.4, 1.8 Hz) 7.24 (1H, d J = 1.8 Hz) 7.88 (1H, s) 11.12 (1H, s )

Example 5

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde (7-chloroquinolin-4-yl) hydrazone

0.50 g (2.27 mmole) of the compound of Reference Example 1 was diluted in 60 ml of ethanol, and then a catalytic amount of concentrated hydrochloric acid was added, followed by stirring at room temperature for 10 minutes. 0.67 g of 7-chloro-4-hydrazinoquinoline was added to the reaction solution, stirred at 45 ° C. for 10 hours, and the resulting precipitate was filtered and washed with 20 ml of ethanol to obtain 0.55 g (61.20%) of the title compound. .

Melting Point: 210 ~ 212 ℃

¹ H NMR (DMSO-d6): 1.61 (2H, m) 1.78 (4H, m) 1.94 (2H, m) 3.81 (3H, s) 4.89 (1H, m)

7.04 (1H, d J = 8.3 Hz) 7.28 (1H, dd, J = 8.3, 1.8 Hz) 7.36 (1H, d J = 5.2 Hz) 7.42 (1H, d J = 1.8 Hz) 7.61 (1H, d) 7.86 (1H, s) 8.39 (1H, s) 8.44 (2H, d J = 9.1 Hz)

Example 6

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde (2-imidazolino) hydrazone

0.50 g (2.27 mmole) of the compound of Reference Example 1 was diluted in 50 ml of ethanol, and then a catalytic amount of concentrated hydrochloric acid was added, followed by stirring at room temperature for 10 minutes. 0.63 g of hydrazino-2-imidazoline hydrobromide was added to the reaction solution, followed by stirring at 45 ° C. for 8.0 hours. The residue obtained by concentrating the solvent under reduced pressure was diluted with dichloromethane and washed twice with 50 ml of distilled water. The separated organic layer was dried over anhydrous acetic acid and distilled under reduced pressure to give a pale yellow oily product. The residue was purified by flash chromatography (silica gel: developing solution 7.5% methanol-dichloromethane) to give 0.45 g (65.56%) of the title compound as white. Got it.

Melting Point: 87 ~ 90 ℃

¹ H NMR (DMSO-d6): 1.61 (2H, m) 1.72 (4H, m) 1.89 (2H, m) 3.70 (4H, s) 3.79 (3H, s)

4.89 (1H, m) 7.01 (1H, d J = 8.4 Hz) 7.24 (1H, dd, J = 8.4, 1.8 Hz) 7.44 (1H, d J = 1.8 Hz) 8.06 (1H, s)

Example 7

(E) -2-[(3-cyclopentyloxy-4-methoxyphenyl) methylene] hydrazinecarboxamide

The reaction was carried out in the same manner as in Example 6, using 0.50 g (2.27 mmole) of the compound of Reference Example 1 as a starting material to obtain 0.47 g (74.66%) of a white title compound.

Melting Point: 144 ~ 146 ℃

¹ H NMR (DMSO-d6): 1.58 (2H, m) 1.71 (4H, m) 1.89 (2H, m) 3.76 (3H, s) 4.92 (1H, m)

6.44 (2H, brs) 6.93 (1H, d J = 8.3 Hz) 7.09 (1H, dd, J = 8.3, 1.9 Hz) 7.36 (1H, d J = 1.9 Hz) 7.75 (1H, s) 10.08 (1H, s )

Example 8

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde (2-nitrophenyl) hydrazone

The reaction was carried out in the same manner as in Example 3 using 0.50 g (2.27 mmole) of the compound of Reference Example 1 to obtain 0.63 g (78.09%) of the title compound in red yellow color.

Melting Point: 135 ℃ Decomposition

¹ H NMR (DMSO-d6): 1.61 (2H, m) 1.77 (4H, m) 1.94 (2H, m) 3.80 (3H, s) 4.88 (1H, m)

6.89 (1H, m) 7.03 (1H, d J = 8.4 Hz) 7.22 (1H, dd, J = 8.4, 1.9 Hz) 7.35 (1H, d J = 1.9 Hz) 7.66 (1H, t J = 1.6 Hz) 7.95 (1H, d J = 8.7 Hz) 8.11 (1H, dd J = 8.5, 1.4 Hz) 8.39 (1H, s) 11.15 (1H, s)

Example 9

(E) -2-[(3-cyclopentyloxy-4-methoxyphenyl) methylene] hydrazinecarbothioamide

Reaction was carried out in the same manner as in Example 6, using 1.00 g (4.54 mmole) of the compound of Reference Example 1 to obtain 0.94 g (70.57%) of the white title compound.

Melting Point: 112 ~ 114 ℃

¹ H NMR (DMSO-d6): 1.57 (2H, m) 1.71 (4H, m) 1.88 (2H, m) 3.76 (3H, s) 4.91 (1H, m)

6.44 (2H, brs) 6.93 (1H, d J = 8.4 Hz) 7.09 (1H, dd, J = 8.4, 1.9 Hz) 7.36 (1H, d J = 1.9 Hz) 7.74 (1H, s) 10.06 (1H, s )

Example 10

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde (4-chlorophenyl) hydrazone

The reaction was carried out in the same manner as in Example 6, using 1.50 g (6.81 mmole) of the compound of Reference Example 1 as a starting material to obtain 1.65 g (70.26%) of a white title compound.

Melting Point: 133 ~ 135 ℃

¹ H NMR (DMSO-d6): 1.60 (2H, m) 1.76 (4H, m) 1.91 (2H, m) 3.78 (3H, s) 4.86 (1H, m)

6.97 (1H, d J = 8.4 Hz) 7.04 (2H, dd J = 6.8, 2.1 Hz) 7.12 (1H, dd, J = 8.4, 1.9 Hz) 7.24 (2H, dd J = 6.8, 2.1 Hz) 7.27 (1H , d J = 1.9 Hz) 7.87 (1 H, s) 10.27 (1 H, s)

Example 11

(E) -2-[(3-cyclopentyloxy-4-methoxyphenyl) methylene] hydrazinecarbonylmethyl (trimethyl) ammonium chloride

The reaction was carried out in the same manner as in Example 3, using 1.50 g (6.81 mmole) of the compound of Reference Example 1 and 1.03 g of (carboxymethyl) trimethylammonium chloride hydrazide as starting materials to obtain 1.73 g (68.68%) of a white title compound. .

Melting Point: 178 ~ 179 ℃

¹ H NMR (DMSO-d6): 1.60 (2H, m) 1.73 (4H, m) 1.90 (2H, m) 3.30 (9H, s) 3.79 (3H, s)

4.33 (2Ha, s) 4.79 (2Ha, s) 4.84 (1H, m) 7.03 (1H, d J = 8.4 Hz) 7.23 (1H, dd, J = 8.4, 1.8 Hz) 7.29 (1H, d J = 1.8 Hz ) 8.01 (1Ha ', s) 8.26 (1Ha', s) 12.05 (1H, brs)

Example 12

(E) -N- (1,4-oxazin-4-yl) -3-cyclopentyloxy-4-methoxyphenylmethaneimine

After diluting 5.0 g (22.7 mmole) of the compound of Reference Example 1 in 50 ml of ethanol and stirring at room temperature for 10 minutes, 2.91 ml of N-aminomorpholine was added to the reaction solution. The reaction solution was stirred at 25 ° C. for 14 hours, the resulting precipitate was filtered, washed with 20 ml of ethanol and the white solid was recrystallized from isopropyl ether to give 6.37 g (92.19%) of the title compound.

Melting Point: 108 ~ 109 ℃

¹ H NMR (DMSO-d6): 1.56 (m, 2H) 1.70 (m, 4H) 1.88 (m, 2H) 3.03 (m, 4H) 3.67 (m, 7H)

4.77 (m, 1H) 6.88 (d, 1H) 7.04 (dd, 1H) 7.18 (d, 1H) 7.62 (s, 1H)

Example 13

(E) -N-piperidino-3-cyclopentyloxy-4-methoxyphenylmethaneimine

In the same manner as in Example 12, using 0.50 g (2.27 mmole) of the compound of Reference Example 1 and 0.31 ml of N-aminopiperidine as a starting material, 0.65 g (94.68%) of the title compound was obtained.

Melting Point: 81 ~ 82 ℃

¹ H NMR (DMSO-d6): 1.52 (m, 4H) 1.67 (m, 8H) 1.90 (m, 2H) 3.04 (m, 4H) 3.70 (s, 3H)

4.76 (m, 1H) 6.89 (d, 1H) 7.04 (dd, 1H) 7.18 (d, 1H) 7.57 (s, 1H)

Example 14

(E) -2-[(3-cyclopentyloxy-4-methoxyphenyl) methylene] hydrazinecarboximidamide

The reaction was carried out in the same manner as in Example 6, using 1.50 g (6.81 mmole) of the compound of Reference Example 1 and 0.73 g of aminoguanidine hydrochloride as a starting material to obtain 1.60 g (85.02%) of the white title compound.

Melting Point: 100 ~ 103 ℃

¹ H NMR (DMSO-d6): 1.62-1.64 (2H, m) 1.74-1.78 (4H, m) 1.94-1.97 (2H, m) 3.84 (3H, s) 4.95-4.98 (1H, m) 7.05 (1H , d J = 8.4 Hz) 7.33 (1H, dd, J = 8.4, 2.0 Hz) 7.54 (1H, d J = 1.9 Hz) 7.7 (1H, brs) 8.36 (1H, s) 11.69 (1H, s)

Example 15

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde (2-pyridinyl) hydrazone

The reaction was carried out in the same manner as in Example 6, using 0.80 g (3.63 mmole) of the compound of Reference Example 1 and 0.39 g of 2-hydrazinopyridine as starting materials to obtain 0.96 g (84.89%) of the white title compound.

Melting Point: 142 ~ 143 ℃

¹ H NMR (DMSO-d6): 1.58-1.61 (2H, m) 1.71-1.76 (4H, m) 1.89-1.94 (2H, m) 3.77 (3H, s) 4.84-4.87 (1H, m) 6.73-6.74 (1H, m) 6.97 (1H, d J = 8.3 Hz) 7.10 (1H, dd, J = 8.3, 1.8 Hz) 7.20 (1H, d J = 8.4 Hz) 7.27 (1H, d J = 1.8 Hz) 7.62 to 7.63 (1H, m) 7.94 (1H, s) 8.09 (1H, dd J = 4.9, 1.0 Hz) 10.67 (1H, s)

Example 16

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde (2-carboxyphenyl) hydrazone

The reaction was carried out in the same manner as in Example 6, using 0.80 g (3.63 mmole) of the compound of Reference Example 1 and 0.66 g of 2-hydrazinobenzoic acid hydrochloride as a starting material to obtain 1.05 g (81.57%) of a white title compound.

Melting Point: 174 ~ 176 ℃

¹ H NMR (DMSO-d6): 1.59-1.60 (2H, m) 1.71-1.76 (4H, m) 1.92-1.93 (2H, m) 3.78 (3H, s) 4.85 (1H, m) 6.78 (1H, dd) J = 7.0, 1.0 Hz) 6.99 (1H, d J = 8.4 Hz) 7.20 (1H, dd, J = 8.4, 1.9 Hz) 7.32 (1H, d J = 1.9 Hz) 7.50 (1H, dd J = 7.0, 1.6 Hz) 7.68 (1H, dd J = 8.5, 0.8 Hz) 7.84 (1H, dd J = 8.0, 1.4 Hz) 8.05 (1H, s) 8.79 (1H, d J = 4.9 Hz) 11.17 (1H, s)

Example 17

(E) -3-cyclopentyloxy-4-methoxybenzaldehyde (4-trifluoromethylpyrimidin-2-yl)

Dragzon

In the same manner as in Example 6, 0.80 g (3.63 mmole) of the compound of Reference Example 1 and 0.63 g of 2-hydrazino-4- (trifluoromethyl) pyrimidine were used as starting materials. 79.62%).

Melting Point: 73 ~ 75 ℃

¹ H NMR (DMSO-d6): 1.58-1.59 (2H, m) 1.72-1.76 (4H, m) 1.89 (2H, m) 3.79 (3H, s)

4.81 to 4.84 (1H, m) 7.01 (1H, d J = 8.4 Hz) 7.19 (1H, dd, J = 8.4, 2.0 Hz) 7.21 (1H, d J = 4.9 Hz) 7.27 (1H, d J = 2.0 Hz ) 8.11 (1H, s) 8.79 (1H, d J = 4.9 Hz) 1.67 (1H, s)

The fact that the pesticide containing the catechol hydrazone derivative of the present invention prepared as described above shows an excellent control effect against hygienic pests and phytoparasites is proved by the following test example. That is, the representative catechol hydrazone derivatives prepared according to the present invention were measured and evaluated for each insecticidal and acaricide activity according to the following test method.

In this case, the test drug solution, that is, the pesticide composition was prepared by using a predetermined amount of the compound, an appropriate amount of the surfactant, water, and acetone. At this time, the first test concentration of the chemical solution was 500ppm, and when the mortality rate was 100%, the concentration was gradually lowered and tested to obtain the LC concentration of ₅₀ , that is, the concentration of the chemical solution (ppm) showing 50% mortality rate.

In addition, the LC ₅₀ value of the compound according to the present invention was tested according to the following test example, and the superiority of the drug was proved by comparing it with the LC ₅₀ value of the control drug which is used worldwide for a particular pest.

Test Example 1

Experiment on Brown Planthopper

Nilaparvata lugens stals were bred in a constant-temperature room without insecticides, and were bred indoors using Dongjin rice. Insecticidal test revealed adult females 4 days after hatching. Six taps of 5 to 7 cm in length (breed: Dongjin) were rolled with cotton wool, inserted into a test tube (3 cm in diameter, 15 cm in height), and 20 adult insects were inoculated. A nozzle of a micro atomizer (a single injection amount of 0.0254 ± 0.000 mL) was placed at the center of the inlet of the test tube, and the 500 ppm suspension was sprayed twice. The control was treated with acetone-surfactant-distilled water solution containing no test agent. Each treatment was performed in three iterations. After treatment, the mortality rate was examined after 24 hours and 48 hours while kept in a constant temperature room. The mortality rate was examined for the test compound using each compound. LC ₅₀ values were obtained for some compounds and commercialized controls that showed 100% mortality at 500 ppm.

Test Example 2

Test for Green peach aphid

Peach aphids (Myzus persicae sulzer) were raised indoors using tobacco (variety: NC-82). Insecticidal tests revealed a nymph The test compound was immersed in 50 ml of 500 ppm test chemical solution (type: NC-82) for 30 seconds, air-dried for 30 seconds, and then air-dried for 30 minutes as described in the preparation of the chemical solution. Put it. The control was immersed in acetone-surfactant-distilled water solution. Each treatment is carried out in three iterations. 20 insects were inoculated into each treated tobacco leaf and stored in a constant temperature room to check for mortality after 24 and 48 hours. The mortality rate was examined for the test compound using each compound. In addition, LC ₅₀ values were obtained for some compounds and commercialized control agents that showed 100% mortality at 500 ppm.

Test Example 3

Test for Diamond-backmoth

Chinese cabbage moth (Plutella xylostella) cultivated with no pesticide in constant temperature room

Linnaeus) was bred indoors using cabbage, and the insecticide test was known to be 3 larvae. Insecticidal test was first deposited for 30 seconds in a cabbage leaf cut into a circular 9cm diameter on the test drug and then air dried for 30 minutes. The control treated with acetone-surfactant-distilled water solution containing no test compound. The treated leaves were placed in a 9 cm diameter Petri dish and inoculated with 10 3 larvae. Each treatment was repeated three times. Petri dishes were covered in lids and kept in a constant temperature room to check mortality after 24 and 48 hours. The mortality rate was examined for the test compound using each compound. LC ₅₀ values were obtained for some compounds and commercialized controls that showed 100% mortality at 500 ppm.

Test Example 4

Test on Tobacco Cutworm

Tobacco spider moth (Spodoptera litura) was raised indoors using cabbage without pesticide selection in a constant temperature room. In the pesticidal test, first, the cabbage leaf cut into 9 cm diameter circular specimen was immersed for 30 seconds and then air dried for 30 minutes. The control was treated with acetone-surfactant-distilled water solution containing no test compound. The treated leaves are placed in a 9 cm diameter Petri dish and inoculated with 10 3 larvae. Each treatment was repeated three times. Petri dishes were covered in lids and kept in a constant temperature room to check mortality after 24 and 48 hours. The mortality rate was examined for the test compound using each compound. In addition, LC ₅₀ values were obtained for some compounds and commercialized control agents that showed 100% mortality at 500 ppm.

Test Example 5

Test for two-spotted spider mite

The pest spotted ongae (Tetranychus urtiae koch) was reared indoors using a kidney bean leaves in a pesticide susceptible system in a constant temperature room. Insecticide test revealed adult. Agar solution (0.5% agar content) is poured into the case to a depth of about 1 cm, the kidney beans are fixed on it, 40 adult seeds are inoculated, and 3 ml of the 500 ppm test solution is sprayed using a fine fraction. The control was sparged with acetone-surfactant-distilled water solution containing no test compound. Each treatment was repeated three times. After treatment, the mortality rate was examined after 24 hours and 48 hours while kept in a constant temperature room. The mortality rate was examined for the test compound using each compound. In addition, LC ₅₀ values were obtained for some compounds and commercialized control agents that showed 100% mortality at 500 ppm.

As a result, the insecticide containing the catechol hydrazone derivative according to the present invention was found to exhibit much better efficacy and broader pesticide range than conventional insecticides such as deltamethrin or permethrin from the LC ₅₀ value of each test collision.

Claims (1)

Insecticide compositions containing a compound of formula (I) or a salt thereof and a carrier commonly used in pesticides in an amount effective to remove pests: (I) In the above formula, R ¹ is C ₁ -C ₇ alkyl or C ₃ -C ₇ cycloalkyl; R ² is —H, —OH, —C ₁ -C ₅ alkyl or —CH ₂ CH ₂ C (═O) NH ₂ ; R ³ or R ⁴ are each independently i) -H, ii) C ₁ -C ₇ alkyl, i) -C (= X) -R ⁵ , i) halogen, C ₁ -C ₆ alkoxy, nitrile, trifluor A 2-, 3- or 4-pyridyl, pyrimidyl or phenyl group optionally substituted with one or two of rommethyl, C ₁ -C ₆ alkyl and carboxylic acid groups, or iii) containing oxygen, sulfur or nitrogen Cyclic compounds directly linked to C ₃ -C ₄ ; X is O, S or NR ⁵ ; R ⁵ is i, -C ₁ -C ₇ alkyl, ii) -NHR ⁶ or iii) 2-, 3- optionally substituted with halogen, nitrile, trifluoromethyl, C ₁ -C ₆ alkyl or carboxylic acid groups Or 4-pyridyl, pyrimidyl or phenyl group; R ⁶ is —H, —OH, —C ₁ -C ₅ alkoxy, —C ₁ -C ₅ alkyl, pyridyl or phenyl group.