JP5076555B2 - Pest control agent - Google Patents

Description

  The present invention relates to a pest control agent useful in the fields of agriculture and horticulture, hygiene and the like.

So far, repellents and insecticides for the purpose of controlling various pests have been developed (Non-patent Document 1 and Non-Patent Document 2). However, these widely used drugs are not always satisfactory in terms of effectiveness and safety.
In addition, the emergence of pests that have acquired resistance to drugs that have been widely used in the past has become a problem, and the control of these resistant pests has become difficult year by year. Furthermore, due to recent changes in the living environment, dust mites, dust mites, dust mites, etc. are generated indoors, causing problems such as causing allergic asthma and skin rash as well as causing discomfort. Although it is known that organophosphorus compounds such as sumithion and diazinon are effective for mites that live indoors, they are not always satisfactory from the viewpoint of safety against human livestock.
Therefore, it is also safe for humans and useful organisms and has little effect on the environment. It also has a pest control effect on various pests that have acquired resistance to conventional pest repellents and insecticides. The development of new drugs is desired.

  Examples of recent research related to the above problems include anilinotriazole derivatives (Patent Document 1), pyrazole derivatives (Patent Document 2), acrylonitrile derivatives (Patent Document 3), and the like. Since it has a complicated structure, there exists a problem that it is difficult to manufacture industrially cheaply.

  In addition, a synthesis method using a special oxidizing agent has been reported for 1-phenyl-4-hydroxy-2-buten-1-one, which is one of alcohol compounds (Non-patent Document 3). However, there has been no report on the use of this compound.

JP 2006-265209 A JP 2006-199637 JP 2005-255571 A "Development of animal repellents", edited by Kiyoshi Akamatsu, Shoji Fujii, Hayashi, Publisher: CMC Publishing, 1999 "Measures against pests in living environment", Editor-in-Chief: Ikuo Tanaka, Publisher: Japan Environmental Health Center, 2000 R. Badri, H. Shalbaf, M.A. Heidary, Synthetic Communications, 31 (22), 3473-3479 (2001).

  An object of the present invention is to provide a pest control agent for new mites, mosquitoes and the like in view of the above situation.

As a result of intensive studies to solve the above problems, the present inventor has found that the ester compound represented by the following formula (1) has excellent pest control activity against mites, mosquitoes and the like, and completed the present invention. It came to let you. That is, the present invention
<1> A pest control agent comprising an ester compound represented by the following general formula (1) as an active ingredient ,

(In formula (1), R ¹ represents a hydrogen atom, a methyl group or a methoxy group,, R ² is also a hydrocarbon group having 1 to 16 carbon atoms include an oxygen atom or a halogen atom.)
<2> The pest control agent according to 1 above, wherein the pest is a tick or a mosquito.
[Effect of the invention]

The ester compound of the present invention has an excellent pest control activity, and the pest control agent characterized by blending such an esterified product as an active ingredient can be used in the fields of agriculture, horticulture and hygiene.
[Best Mode for Carrying Out the Invention]

First, the compound represented by the general formula (1) will be described.
In the present invention, R ¹ in the formula (1) is a hydrogen atom, a methyl group, or a methoxy group, and a hydrogen atom or a methyl group is preferable. When R ¹ is a methyl group or a methoxy group, the bonding position is effective at any of the o-position, m-position, and p-position with respect to the unsaturated ketone group. Is preferred.

R ^{2 in the} formula (1) is a hydrocarbon group having 1 to 16 carbon atoms which may contain an oxygen atom or a halogen atom. The hydrocarbon group is a linear alkyl group, an alkyl group having a branch, an alkyl group having an unsaturated bond, a cyclic alkyl group, an aralkyl group (Aralkyl), or an araalkyl group having an alkyl group. Are methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl , Nonyl group, decyl group, benzyl group, phenethyl group, 3-phenylpropyl group, 2- (p-tolyl) -ethyl group, 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropyl group , Phenyl group, m-tolyl group, etc., preferably methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, A butyl group, an isobutyl group, and a 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropyl group.

  Examples of the hydrocarbon group containing a halogen atom include a chloromethyl group, 3-chloropropyl group, 3-bromopropyl group, m-chlorophenyl group, 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropyl group. 3- [2-chloro-2- (4-chlorophenyl) ethenyl] -2,2-dimethylcyclopropyl group, 3- (2,2-dibromoethenyl) -2,2-dimethylcyclopropyl group, 2, 2-dimethyl-3- (2-chloro-3,3,3-trifluoro-1-propenyl) cyclopropyl group and the like are exemplified, and preferably 3- (2,2-dichloroethenyl) -2,2 -Dimethylcyclopropyl group, 3- [2-chloro-2- (4-chlorophenyl) ethenyl] -2,2-dimethylcyclopropyl group, 3- (2,2-dibromoethenyl) -2 - dimethylcyclopropyl group, a 2,2-dimethyl-3- (2-chloro-3,3,3-trifluoro-1-propenyl) cyclopropyl group.

  Examples of the hydrocarbon group containing an oxygen atom include benzyloxymethyl group, L-mentoxymethyl group, phenoxymethyl group, 4-phenoxybutyl group, p-methoxyphenoxymethyl group, p-hydroxyphenoxymethyl group, and 4-methoxy. A butyl group can be exemplified, and an L-menthoxymethyl group is preferred.

Further, in such a hydrocarbon group containing a hydrocarbon group or a halogen atom described above, if asymmetric carbon atoms are present, as long as they do not impair the pest control activity, optically active forms, also Re not have racemic mixtures included in the present invention It is. As the pest control agent of the present invention, the compound represented by the general formula (1) may be used alone, or a plurality of mixtures may be used.

Below, the manufacturing method of the ester compound represented by General formula (1) of this invention is demonstrated. The compound represented by the general formula (1) is, for example, 1-phenyl-4-hydroxy-2-buten-1-one, R ² (R ² is a carbon atom which may contain the above-described oxygen atom or halogen atom). It can be easily produced by reacting with a carboxylic acid having a residue (which represents a hydrogen group) or a derivative thereof by a known method. As this known esterification method, for example, a method described in books such as [Edited by The Chemical Society of Japan, 5th edition, Experimental Chemistry Course, Volume 16, Synthesis of Organic Compounds IV (pages 35-45), Maruzen] Is mentioned. Specifically, a method using a carboxylic acid and a dehydration condensing agent, a method using a carboxylic acid and an acid catalyst, a method using a halide of a carboxylic acid, a method using a carboxylic acid anhydride, and the like can be used.

Next, the production method will be specifically described with a method using carboxylic acid chloride as a representative example. That is, for example, for 1-phenyl-4-hydroxy-2-buten-1-one, R ² COCl in the presence of a basic substance (R ² represents a hydrocarbon group that may contain the above-described halogen atom). It can manufacture by making this react.
In this production method, the amount of carboxylic acid chloride is basically a stoichiometric amount with respect to, for example, 1-phenyl-4-hydroxy-2-buten-1-one, and the reactivity is taken into consideration. The stoichiometric amount is 0.5 to 2.0 times, preferably 0.8 to 1.2 times. If the amount of the carboxylic acid peroxide used is too small, the progress of the reaction is insufficient, and if the amount used is too large, the cost increases and the side reaction tends to proceed, which is not preferable.

  Examples of basic substances used in this production method are sodium carbonate and potassium carbonate. Examples include inorganic basic substances such as sodium hydroxide, organic amines such as triethylamine, diisopropylethylamine, N, N-dimethylaminopyridine, and 1-methylimidazole, and metal alkoxides such as sodium methoxide and potassium t-butoxide. Organic amines such as triethylamine and diisopropylethylamine can be preferably used.

  In this production method, the amount of the basic substance is, for example, 0.5 to 3 equivalents relative to 1-phenyl-4-hydroxy-2-buten-1-one, and preferably 1.0 to 1. 5 equivalents. If the amount of the basic substance is too small, the progress of the reaction becomes insufficient, and if the amount used is too large, the cost increases, which is not preferable.

  This production method is preferably carried out in a solvent, halogen solvents such as dichloromethane and carbon tetrachloride, aromatic solvents such as toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane. An ester solvent such as ethyl acetate, a ketone solvent such as acetone or methyl ethyl ketone, a nitrile solvent such as acetonitrile, or a mixed solvent thereof can be used. In view of the reaction yield, an aromatic solvent is preferable, and use of toluene is particularly preferable.

In this production method, the reaction temperature varies depending on the R ² COCl and basic substance used and the amount used, but can be -20 ° C to 90 ° C, preferably -5 ° C to 60 ° C. When the reaction temperature is too low, the progress of the reaction is slow, and when it is too high, the side reaction tends to proceed, which is not preferable.
In this production method, the reaction time varies depending on conditions, but is usually from several minutes to several hours.

  In this production method, after completion of the reaction, the compound represented by the general formula (1) can be separated and purified by a conventionally known method such as solvent extraction, column chromatography, crystallization method, distillation or the like.

  The compound represented by the formula (1) of the present invention can be used as a pest control agent. Examples of the pests include hygiene fields (eg, cockroaches, flies, fleas, lice, bees, ants, centipedes, millipedes, etc.), and horticultural ticks (eg, dust mites, claw mites, dust mites, dust mites, spider mites, etc.) ) And mosquitoes, and dust mites, spider mites, and mosquitoes are more preferable as targets, and dust mites and spider mites are more preferable. This control indicates that it may be killed, repelled, or knocked down.

  In the present invention, when the compound represented by the formula (1) is used as a pest control agent, the effective content and the use amount are the use form, the use form, the type of pest to be used, and their expected It can be changed over a wide range according to conditions such as the time of occurrence and period.

In the present invention, the compound represented by the formula (1) alone exhibits excellent pest control, for example, acaricidal activity. When the compound represented by the formula (1) of the present invention is used as a pest control agent, it can be used alone or in combination with other pest control agents, acaricides and the like. When the compound represented by the formula (1) of the present invention is used as a pest control agent, the concentration used varies depending on the target pest. The concentration when the compound represented by the formula (1) of the present invention is used as a pest control agent, for example, an acaricide, is preferably 0.01 to 50% by weight, preferably 0.1 to 10% by weight in the preparation. Is more preferable. If the concentration is less than 0.01% by weight, the effect of the present invention cannot be obtained sufficiently, and if it exceeds 50% by weight, it is not preferable because it is disadvantageous in terms of formulation or cost. Moreover, when using as a tick repellent, it is preferable that it is 0.001 to 20 weight% in a formulation, and 0.03 to 10 weight% is more preferable. If the concentration is less than 0.001% by weight, a repellent effect may not be obtained sufficiently, which is not preferable. When using as a mosquito knockdown agent, it is preferable that it is 0.01 to 50 weight% in a formulation, and 0.1 to 10 weight% is more preferable. If the concentration is less than 0.01% by weight, the effects of the present invention may not be sufficiently obtained, which is not preferable.
However, in special cases, it is possible to exceed these ranges. For example, when a synergistic effect or an additive effect is observed when used in combination with other insect pest control agents and acaricides, they can be used at lower doses than those described above.

  In the present invention, the form as a pest control agent, acaricide, etc. is not particularly limited and may be used in any form such as powder, granule, tablet, solution, emulsion, suspension, etc. Can do. For example, the compound represented by the formula (1) of the present invention can be used by appropriately supporting it on clays, solids or liquids, and if necessary, other components such as a surfactant are blended, It can also be used as an emulsion, wettable powder, granular material, powder, spray, aerosol and the like. Furthermore, normal effective bases may be used according to the form of the pest control agent and the acaricide, such as solvents, pH adjusters, bactericides, preservatives, fragrances, colorants, antioxidants, binders. Etc. can also be blended.

Embodiment An mite repellent characterized by containing an ester compound represented by the general formula (1) as an active ingredient.
A mosquito knockdown agent comprising an ester compound represented by the general formula (1) as an active ingredient.
An agrochemical for agricultural and horticultural use comprising an ester compound represented by the general formula (1) as an active ingredient.

<Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. % Represents weight%.

<Synthesis Example 1>
-Synthesis of 1-phenyl-4-hydroxy-2-buten-1-one (compound 1)
3-Chloroperbenzoic acid (273 mmol) was added to a solution of 1-phenyl-3-buten-1-one (200 mmol) in dichloromethane (600 ml). This was heated to reflux for 5 hours and then allowed to cool. Thereafter, the organic layer was washed successively with a 10% aqueous sodium thiosulfate solution (200 ml) and a 10% aqueous sodium carbonate solution (350 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
Next, the obtained residue was dissolved in acetone (200 ml), a solution prepared by previously dissolving triethylamine (101 mmol) and acetic acid (201 mmol) in acetone (200 ml) was added, and the mixture was stirred at 50 ° C. After 1 hour, the mixture was allowed to cool and the solvent was distilled off under reduced pressure. The residue was partitioned by adding chloroform (300 ml) and 10% aqueous sodium carbonate solution (200 ml). The organic layer was collected and the aqueous layer was extracted 3 times with chloroform (50 ml). The combined organic layers were dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography, and then recrystallized from toluene to obtain colorless needle crystal compound 1 (the following formula (2)) (19.0 g, yield 59%).

○ Physicochemical properties of Compound 1 Melting point 82.0-82.7 ℃
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 2.59 (1H, br), 4.73 (2H, s), 7.14 (1H, m), 7.25 (1H, m), 7.47 (2H, m), 7.75 (1H , m), 7.97 (2H, d, J = 7.6 Hz).
IR (ATR method) cm ^-1 : 3431, 1657, 1608, 1594, 1575, 1288, 1219, 1098, 753.
MS (m / z): 163 (M ⁺ ).
UV λ _max (MeOH) nm (ε): 256 (20000).
[Exemplary Synthesis Example 1]

○ Synthesis of cyclopropanecarboxylic acid ester (compound 2) To a suspension of 1-phenyl-4-hydroxy-2-buten-1-one (compound 1, 61.7 mmol) and triethylamine (64.6 mmol) in toluene (200 ml) Under ice-cooling, cyclopropanecarboxylic acid chloride (63.9 mmol) was added. After 2 hours at room temperature, the reaction was stopped by adding distilled water (50 ml) and partitioned. The organic layer was separated and washed successively with saturated aqueous sodium hydrogen carbonate solution (50 ml) and saturated brine (50 ml). The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography and further distilled under reduced pressure to obtain colorless liquid compound 2 (the following formula (3)) (9.76 g, yield 69%).

○ Physicochemical properties of Compound 2 Boiling point 147-150 ℃ (0.3 mmHg)
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 0.94 (2H, dt, J = 4.8 and 8.0 Hz), 1.07 (2H, m), 1.72 (1H, m), 4.86 (2H, dd, J = 1.6 and 4.0 Hz), 7.01 (1H, dt, J = 15.6 and 4.0 Hz), 7.10 (1H, m), 7.49 (2H, t, J = 7.2 Hz), 7.58 (1H, t, J = 7.2 Hz), 7.94 (2H, m)
IR (ATR method) cm ^-1 : 1727, 1674, 1628, 1282, 1264, 1160, 1098, 754.
MS (m / z): 231 (M ⁺ ).
UV λ _max (MeOH) nm (ε): 254 (17000).
Anal.Calcd for C ₁₄ H ₁₄ O ₃ : C, 73.01; H, 6.14.Found: C, 72.74; H, 6.25.
[Exemplary Synthesis Example 2]

○ Synthesis of acetate ester (compound 3) 1-phenyl-4-hydroxy-2-buten-1-one (compound 1, 52.3 mmol) and triethylamine (53.1 mmol) in toluene (200 ml) suspension in ice-cooled Acetic anhydride (52.9 mmol) was added under. Next, N, N-dimethylaminopyridine (2.62 mmol) was added, and after 1 hour at room temperature, distilled water (50 ml) was added to stop the reaction and partition. The organic layer was separated and washed successively with saturated aqueous sodium hydrogen carbonate solution (50 ml) and saturated brine (50 ml). The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain pale yellow liquid compound 3 (the following formula (4)) (10.3 g, yield 96%).

○ Physicochemical properties of Compound 3 Boiling point 128-131 ℃ (0.2 mmHg)
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 2.16 (3H, s), 4.85 (2H, dd, J = 1.6 and 4.4 Hz), 7.01 (1H, dt, J = 15.6 and 4.4 Hz), 7.10 (1H , dt, J = 15.6 and 1.6 Hz), 7.49 (2H, m), 7.58 (1H, m), 7.94 (2H, m)
IR (ATR method) cm ^-1 : 1739, 1675, 1628, 1283, 1222, 1211, 1081, 755.
MS (m / z): 205 (M ⁺ ).
UV λ _max (MeOH) nm (ε): 254 (17000).
Anal. Calcd for C ₁₂ H ₁₂ O ₃ : C, 70.56; H, 5.93. Found: C, 70.35; H, 6.03.
[Exemplary Synthesis Example 3]

○ Synthesis of m-chlorobenzoate (compound 4) Suspension of 1-phenyl-4-hydroxy-2-buten-1-one (compound 1, 128 mmol) and triethylamine (143 mmol) in toluene (300 ml) Was added m-chlorobenzoic acid chloride (133 mmol). After stirring at room temperature for 1 hour, the reaction was stopped by adding distilled water (100 ml) and partitioned. The organic layer was separated and washed successively with saturated aqueous sodium hydrogen carbonate solution (100 ml) and saturated brine (50 ml). The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain 22.2 g (yield: 52%) of Compound 4 (formula (5) below) as colorless needle crystals. The mother liquor was subjected to silica gel column chromatography to obtain 13.9 g (yield 32%) of compound 4 (the following formula (5)).

○ Physicochemical properties of Compound 4 Melting point: 79.4-80.5 ℃
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 5.11 (2H, t, J = 4.0 Hz), 7.13 (2H, m), 7.46 (1H, dt, J = 8.4 and 16.0 Hz), 7.57 (2H, d , J = 1.2 Hz), 7.59 (2H, dd, J = 5.6 and 7.6 Hz), 7.94 (2H, dd, J = 1.2 and 8.4 Hz), 7.99 (1H dt, J = 1.2 and 6.8 Hz), 8.08 ( (1H, t, J = 1.2Hz)
IR (ATR method) cm ^-1 : 1716, 1668, 1623, 1577, 1278, 1260, 745, 738.
MS (m / z): 301 (M ⁺ ).
UV λ _max (MeOH) nm (ε): 225 (shoulder, 31000), 230 (shoulder, 29000), 239 (26000), 257 (29000).
[Exemplary Synthesis Example 4]

-Synthesis of benzoic acid ester (compound 5) (Part 1)
To a suspension of 1-phenyl-4-hydroxy-2-buten-1-one (compound 1, 92.5 mmol) and triethylamine (100 mmol) in toluene (250 ml) was added benzoic acid chloride (94.8 mmol). After 3 hours at room temperature, the reaction was stopped by adding distilled water (100 ml) and partitioned. The organic layer was separated and washed successively with saturated aqueous sodium hydrogen carbonate solution (100 ml) and saturated brine (50 ml). The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain 15.4 g (yield 63%) of Compound 5 (formula (6) below) as colorless massive crystals.

○ Physicochemical properties of Compound 5 Melting point: 104.2-105.2 ℃
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 5.11 (2H, t, J = 3.6 Hz), 7.14 (2H, m), 7.48 (4H, m), 7.58 (2H, m), 7.93 (2H, d , J = 7.2 Hz), 8.11 (2H, dd, J = 1.2 and 8.0 Hz)
IR (ATR method) cm ^-1 : 1711, 1666, 1624, 1594, 1276, 1124, 751.
MS (m / z): 267 (M ⁺ ).
UV λ _max (MeOH) nm (ε): 232 (25000), 254 (shoulder, 21000).
[Example Synthesis Example 5]

-Synthesis of benzoic acid ester (compound 5) (2)
The same operation as in Example Synthesis Example 4 was performed except that the reaction solvent was changed from toluene to tetrahydrofuran to obtain Compound 5 in a yield of 34%.
[Exemplary Synthesis Example 6]

○ Synthesis of isovaleric acid ester (compound 6) 1-phenyl-4-hydroxy-2-buten-1-one (compound 1, 61.7 mmol), triethylamine (64.6 mmol) in toluene (200 ml) suspension in ice Isovaleryl chloride (64.0 mmol) was added dropwise under cooling. After 2 hours at room temperature, the reaction was stopped by adding distilled water (50 ml) and partitioned. The organic layer was separated and washed successively with 10% aqueous sodium carbonate solution (50 ml) and saturated brine (50 ml). The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain pale yellow liquid compound 6 (the following formula (7)) (14.1 g, yield 93%).

○ Physicochemical properties of Compound 6 Boiling point 142-146 ℃ (0.2 mmHg)
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 1.01 (6H, d, J = 6.4 Hz), 2.17 (1H, tq, J = 6.4 and 7.2 Hz), 2.30 (2H, d, J = 7.2 Hz), 4.86 (2H, dd, J = 1.6 and 4.4 Hz), 7.01 (1H, dt, J = 15.6 and 4.4 Hz), 7.10 (1H, dt, J = 15.6 and 1.6 Hz), 7.49 (2H, m), 7.58 (1H, m), 7.94 (2H, m)
IR (ATR method) cm ^-1 : 1736, 1676, 1629, 1284, 1180, 1165, 1120, 1099, 756.
MS (m / z): 247 (M ⁺ ).
UV λ _max (MeOH) nm (ε): 254 (18000).
[Exemplary Synthesis Example 7]

○ Synthesis of Isobutyric Acid Ester (Compound 7) Except for changing isovaleryl chloride to isobutyric acid chloride, the same operation as in Example Synthesis Example 6 was performed to obtain pale yellow liquid compound 7 (the following formula (8)). Obtained (yield 98%).

○ Physicochemical properties of Compound 7 Boiling point 135-137 ℃ (0.2 mmHg)
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 1.24 (d, 6H, J = 6.8 Hz), 2.68 (sex, 1H, J = 6.8 Hz), 4.85 (dd, 1H, J = 1.2 and 4.0 Hz), 7.01 (dt, 1H, J = 4.0 and 15.2 Hz), 7.10 (1H, m), 7.47 (2H, t, J = 8.0 Hz), 7.57 (t, 1H, J = 7.2 Hz), 7.93 (2H, m )
IR (ATR method) cm ^-1 : 1734, 1675, 1629, 1283, 1187, 1149, 1095, 754.
MS (m / z): 233 (M ⁺ ).
UV λ _max (MeOH) nm (ε): 253 (16000).
Anal.Calcd for C ₁₄ H ₁₆ O ₃ : C, 72.41; H, 6.97. Found: C, 72.41; H, 7.03.
[Exemplary Synthesis Example 8]

Synthesis of 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid ester (Compound 8)
To a toluene (150 ml) solution of Enamine Chrysanthemic acid (racemic mixture, 30.0 mmol), N, N-dimethylaminopyridine (6.00 mmol) and triethylamine (9.00 ml, 64.6 mmol) under ice-cooling, methanesulfonyl chloride ( 31.0 mmol) was added dropwise. After stirring for 10 minutes, 1-phenyl-4-hydroxy-2-buten-1-one (Compound 1, 30.0 mmol) was added, and the mixture was stirred at room temperature. After 3 hours, distilled water (50 ml) was added to stop the reaction and partition. The organic layer was separated and washed successively with 10% aqueous sodium carbonate solution (50 ml) and saturated brine (50 ml). The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain a pale yellow liquid compound 8 (the following formula (9)) (yield 42%).

-Physicochemical properties of compound 8
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 1.24 (6H, m), 1.50 (0.7H, d, J = 5.2 Hz), 1.74 (6.3H, m), 1.97 (0.3H, m), 2.12 ( 0.7H, m), 4.83 (0.6H, s), 4.86 (1.4H, d, J = 3.6 Hz), 4.93 (0.7H, d, J = 7.6 Hz), 5.38 (0.3H, d, J = 8.4 Hz), 7.05 (2H, m), 7.48 (2H, t, J = 7.6 Hz), 7.58 (1H, t, J = 7.6 Hz), 7.94 (2H, d, J = 7.6 Hz).
IR (ATR method) cm ^-1 : 1726, 1676, 1629, 1282, 1154, 1135, 1114, 756.
MS (m / z): 313 (M ⁺ ).
UV λ _max (MeOH) nm (ε): 254 (17000).
Anal. Calcd for C ₂₀ H ₂₄ O ₃ : C, 76.88; H, 7.76. Found: C, 76.78; H, 7.96.

<Synthesis Example 2>
-Synthesis of 1- (4-methylphenyl) -4-hydroxy-2-buten-1-one (compound 9)
To a solution of 1- (4-methylphenyl) -3-buten-1-one (173 mmol) in dichloromethane (600 ml) was added 3-chloroperbenzoic acid (222 mmol). After heating at reflux for 3 hours, the mixture was allowed to cool. The organic layer was washed sequentially with a 10% aqueous sodium thiosulfate solution (200 ml) and a 10% aqueous sodium carbonate solution (300 ml). After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure.
Next, the obtained residue was dissolved in acetone (200 ml), a solution prepared by previously dissolving triethylamine (87.6 mmol) and acetic acid (175 mmol) in acetone (200 ml) was added, and the mixture was stirred at 50 ° C. After 1 hour, the mixture was allowed to cool and the solvent was distilled off under reduced pressure. The residue was partitioned by adding chloroform (200 ml) and 10% aqueous sodium carbonate (150 ml). The organic layer was collected and the aqueous layer was extracted 3 times with chloroform (50 ml). The combined organic layers were dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography and then recrystallized from toluene to obtain colorless plate crystal compound 9 (the following formula (10)) (12.7 g, yield 42%).

○ Physical and chemical properties of Compound 9 Melting point 61.7-62.6 ℃
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 1.90 (1H, t, J = 6.0 Hz), 2.42 (3H, s), 4.74 (2H, m), 7.12 (1H, dt, J = 3.6 and 15.6 Hz ), 7.22 (1H, d, J = 15.6 Hz), 7.27 (2H, d, J = 8.0 Hz), 7.89 (2H, d, J = 8.0 Hz).
IR (ATR method) cm ^-1 : 3418, 1661, 1611, 1598, 1566, 1287, 1224, 1100, 786.
MS (m / z): 177 (M ⁺ ).
[Example Synthesis Example 9]

○ Synthesis of 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid ester (compound 10)
To a solution of Enamine Chrysanthemic acid (racemic mixture, 51.1 mmol), N, N-dimethylaminopyridine (5.11 mmol) and triethylamine (108 mmol) in toluene (150 ml), methanesulfonyl chloride (51.7 mmol) under ice-cooling Was dripped. After stirring for 10 minutes, 1- (4-methylphenyl) -4-hydroxy-2-buten-1-one (Compound 9, 51.1 mmol) was added and stirred at room temperature. After 18 hours, the reaction was stopped by adding distilled water (50 ml) and partitioned. The organic layer was separated and washed successively with 10% aqueous sodium carbonate solution (50 ml) and saturated brine (50 ml). The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain pale yellow liquid compound 10 (the following formula (11)) (yield 46%).

-Physicochemical properties of compound 10
¹ H-NMR (CDCl ₃ , 400 MHz) δppm: 1.24 (6H, m), 1.50 (0.7H, d, J = 5.2 Hz), 1.74 (6.3H, m), 1.96 (0.3H, m), 2.12 ( 0.7H, m), 2.42 (3H, s), 4.82 (0.6H, d, J = 4.0 Hz), 4.85 (1.4H, d, J = 3.2 Hz), 4.93 (0.7H, d, J = 8.0 Hz) ), 5.38 (0.3H, d, J = 8.0 Hz), 7.03 (2H, m), 7.28 (2H, d, J = 8.0 Hz), 7.86 (2H, d, J = 8.0 Hz)
IR (ATR method) cm ^-1 : 1726, 1673, 1629, 1606, 1283, 1155, 1135, 1114, 796.
MS (m / z): 327 (M ⁺ ).
Anal. Calcd for C ₂₁ H ₂₆ O ₃ : C, 77.25; H, 8.04. Found: C, 77.25; H, 8.21.
[Example 1 ]

○ Activity test against mites
(1) Compound 2 synthesized in Example Synthesis Example 1 was diluted with acetone to prepare 5% and 1% solutions, which were used as specimen dilutions.
(2) The sample dilution was uniformly treated dropwise by 0.5ml to filter paper 10 cm × 10 cm (each processing amount is equivalent to 2.5 g / m ² and 0.5 g / m ² as an active ingredient), room temperature The sample was air-dried for about 1 hour at the bottom (sample area). Further, the same treatment was performed with acetone alone, and used as a control group.
(3) The treated filter paper was cut into half (10 × 5 cm square), folded in half so that the short sides were aligned, and two sides of the open part were sealed to form a bag. About 50 to 100 mushroom leopard mites were released into the bag from the remaining open portion, and immediately covered with a clip to prepare a test group so that mites could not escape.
(4) The test section prepared in (3) above was stored at room temperature and a relative humidity of 90% or more. In addition, the test group provided the group which preserve | saved 24 hours, and the group which preserve | saved 48 hours, and observed the life and death of the tick tested after completion | finish of each preservation | save time with the stereoscopic microscope. At that time, the fine tick was counted as a raw tick.
(5) Each test was carried out in 3 sections in 1 ward, the average lethality was calculated, and the corrected lethality was calculated by the following formula.
Lethality rate (%) = 100 x (lethal number) / (number of samples)
Corrected fatality rate (%) = 100 × (TC) / (100−C)
However, C is the average lethality rate (%) of the control group, and T is the average lethality rate (%) of the sample group.

Table 1 shows the corrected lethality rate (%) of Compound 2 against the mushroom mite. Compound 2 obtained a corrected lethality of 90% or more after 48 hours even at a treatment amount of 0.5 g / m ² , and was found to have good acaricidal activity against the dust mite.

[Example 2 ]

○ Repellent efficacy test against discolored mites
(1) Spread the medium on which the leopard mite is propagating on a 15 x 20 x 3 cm hollow bat, place a piece of gauze cut into 15 x 20 cm on it, place it in a plastic sealed container and keep the humidity. It was stored at a temperature of 90% or more and 20 to 25 ° C.
(2) Compound 2 synthesized in Example Synthesis Example 1 was diluted with acetone to prepare 5% and 1% solutions, which were used as specimen dilutions.
(3) The sample diluent is treated uniformly by 0.5ml in 10 × 10 cm of the filter paper (each processing amount is equivalent to 2.5 g / m ² and 0.5 g / m ² as an active ingredient), 1 hour The sample that had been air-dried to the extent was used as the sample group, and the same treatment was performed with acetone alone, which was used as the control group.
(4) After confirming that many leopard mites in the medium climbed on the case, the specimen group cut into 4.5 × 4.5 cm and the control group were placed one by one on the gauze.
(5) Place black image paper cut into 3 cm square on the filter paper and observe the number of mites that crawls up on the surface of black image paper after 30 minutes. A total of 7 times every 24 hours and a total of 8 times after 24 hours.
(6) Use a new black image paper cut into 3 cm squares for each observation, and if the number of mites rises and is distributed on the black image paper on average, 1/2 or 1/4 of the surface area. The number of mites was counted as 2 or 4 times.
(7) The test was repeated 3 times, and the repelling index was calculated from the obtained result (total number of 3 repetitions) by the following formula.
Repellent index = {(C−T) / C} × 100
However, C is the number of mites rising in the control group, and T is the number of mites rising in the sample group.

Table 2 shows the repellent index of Compound 2 against the dust mite. Compound 2 maintained a repellent index of about 90% from 1 hour to 24 hours at a treatment amount of 2.5 g / m ² , and was confirmed to have a repellent effect against the dust mite.

[Example 3 ]

○ Residue contact test for squid
(1) Compound 2 synthesized in Example Synthesis Example 1 and Compound 4 synthesized in Example Synthesis Example 3 were diluted with acetone to prepare a 5% solution, and 0.5 ml or 1 ml was evenly added dropwise to a filter paper having a diameter of 11 cm. treated was dried for about 1 hour air (corresponding to 2.5 g / m ² or 5 g / m ^2, respectively).
(2) The squid was anesthetized and about 15 animals were placed in a flat dish.
(3) After confirming that the squid was awakened from anesthesia, the filter paper prepared in (1) was slid into the bottom of the petri dish, and the squid was brought into contact with the residue surface.
(4) The test was carried out in a control group treated only with acetone, and each group was run in triplicate. Knockdown of Culex squid over time from the point of contact with the filter paper residue surface treated with chemicals. The number was recorded.

  Table 3 shows the knockdown rate of the compound of the present invention obtained from the above test against Culex mosquito. In particular, Compound 2 was found to have good knockdown efficacy.

  The compounds of the present invention can be easily produced, have pest control activities such as acaricidal activity, and have high utility value.

Claims (2)

A pest control agent comprising an ester compound represented by the following general formula (1) as an active ingredient.
(In formula (1), R ¹ represents a hydrogen atom, a methyl group or a methoxy group,, R ² is also a hydrocarbon group having 1 to 16 carbon atoms include an oxygen atom or a halogen atom.) The pest, pest control agent of claim 1 wherein the mites or mosquitoes.