JP2002187881A - Pyridine compound, controlling agent for harmful arthropod including the same and intemediate for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound excellent in controlling activity to a pest. SOLUTION: This compound is a pyridine compound expressed by general formula (1). [In the formula, R1 and R2 are each same or different a halogen atom or a 1-4C haloalkyl group, n and m are each same or different integer of 1-3. With the proviso that m is the integer of >=2 then R1 is same or different and n is the integer of >=2 then R2 is same or different. R3 is H, NR4R5 (R4 and R5 are each same or different H or the like) or N=CR7R8 (R7 is H or the like, R8 is a 1-4C alkoxy group or the like.)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a pyridine compound,
The present invention relates to an arthropod pest control agent containing the active ingredient as an active ingredient and an intermediate thereof.

[0002]

2. Description of the Related Art Conventionally, the development of arthropod pest control agents has been widely promoted and many drugs have been put to practical use, but their efficacy may not always be sufficient. On the other hand, when the same kind of drug is continuously used for pests, a problem of drug resistance often occurs. Therefore, in the field of arthropod pest control agents, there is a demand for the development of new drugs having sufficient efficacy.

[0003]

In view of such circumstances, the present inventors have conducted intensive studies to find a compound having excellent arthropod pest control activity, and as a result, have a general formula 3

Embedded image [Wherein, R ¹ and R ² are the same or different and represent a halogen atom or a C1-C4 haloalkyl group, and n and m are the same or different and represent an integer of 1-3. However, when m represents an integer of 2 or more, R ¹ may be the same or different, and when n represents an integer of 2 or more, R ² may be the same or different. R ³ is a hydrogen atom, NR ⁴ R
⁵ ｛R ⁴ and R ⁵ are the same or different and are each a hydrogen atom, C1-
C4 alkyl group, C2-C5 alkoxyalkyl group, C
3-C4 alkanoyloxyalkyl group, C (= O) R
⁶ (R ⁶ represents a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C2-C4 alkoxyalkyl group, a C2-C4 alkoxycarbonyl group or a C3-C4 alkanoyloxyalkyl group)} or N = CR ⁷ R ⁸ (R ⁷ represents a hydrogen atom or a C1-C4 alkyl group, R ⁸ is C1-
Represents a C4 alkoxy group or an optionally substituted phenyl group. ). The present invention has been found that the pyridine compound represented by the formula (1) has an excellent arthropod pest control activity. That is, the present invention relates to a compound represented by the general formula (hereinafter, referred to as the present compound), a harmful arthropod controlling agent containing the present compound as an active ingredient (hereinafter, a harmful arthropod controlling agent of the present invention) And a general formula 4 which is an intermediate for producing the compound of the present invention.

Embedded image (Wherein, R ¹ , R ² , m and n have the same meanings as described above).

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound of the present invention, examples of the halogen atom in R ¹ and R ² include a fluorine atom and a chlorine atom, and examples of the C1-C4 haloalkyl group include a trifluoromethyl group and a chlorodifluoromethyl Group, dichlorofluoromethyl group, perfluoroethyl group, perfluoropropyl group and perfluorobutyl group. Examples of the substituent at the 4-position of pyridine include 4-fluoro-3-trifluoromethylphenoxy, 4-chloro-3-trifluoromethylphenoxy, 4-bromo-3-trifluoromethylphenoxy, and 3 -Trifluoromethylphenoxy group, and the substituent at the 2-position of pyridine is, for example, 4
-Fluoro-3-trifluoromethylphenoxy group, 4
-Chloro-3-trifluoromethylphenoxy group, 4-
Bromo-3-trifluoromethylphenoxy group and 3-
A trifluoromethylphenoxy group.

The C 1 -C ⁴ alkyl groups for R ⁴ and R ⁵ include, for example, methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, sec-butyl and tert-butyl;
5 alkoxyalkyl groups include a methoxymethyl group,
Ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, isobutyloxymethyl group, and sec-butyloxymethyl group,
Examples of the C3-C4 alkanoyloxyalkyl group include an acetyloxymethyl group and a propionyloxymethyl group.

The C1 to C4 alkyl group for R ⁶ includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
And a tert-butyl group. Examples of the C1-C4 haloalkyl group include a trifluoromethyl group, a chlorodifluoromethyl group, a dichlorofluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group. Examples of the C2 to C4 alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and an isopropoxymethyl group. Examples of the C2 to C4 alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. , A propoxycarbonyl group, and an isopropoxycarbonyl group. Examples of the C3-4 alkanoyloxymethyl group include an acetyloxymethyl group,
And a propionyloxymethyl group.

[0007] As the C1~C4 alkyl group in R ^7, for example a methyl group, an ethyl group, and propyl group.

The C1-C4 alkoxy group for R ⁸ includes, for example, a methoxy group, an ethoxy group and a propoxy group, and the optionally substituted phenyl group includes, for example, a (C1-C4 alkyl group, a halogen atom,
1-C4 alkoxy group, C1-C4 haloalkyl group, C
A phenyl group, which may be substituted with a 1-C4 haloalkoxy group or a C1-C4 alkylthio group, and specifically, for example, a phenyl group, a 4-methylphenyl group,
-Chlorophenyl group, 4-ethoxyphenyl group, 4-trifluoromethylphenyl group, 3,4-methylenedioxyphenyl group, 4-trifluoromethoxyphenyl group and 4-methylthiophenyl group.

The compounds of the present invention include, for example, the following. A compound wherein the 2-position of the pyridine ring is (optionally substituted 3-trifluoromethylphenoxy group); a compound wherein the 4-position of the pyridine ring is (optionally substituted 3-trifluoromethylphenoxy group); a pyridine ring A compound in which the 2- and 4-positions are (optionally substituted 3-trifluoromethylphenoxy groups); a pyridine ring 2
Compound in which the 4-position is 4-halo-3-trifluoromethylphenoxy group; compound in which the 4-position of the pyridine ring is 4-halo-3-trifluoromethylphenoxy group; 4-halo-3 in the 2-position and 4-position of the pyridine ring -A compound which is a trifluoromethylphenoxy group

The compound of the present invention is described, for example, in the following (Production method 1).
To (Production method 6).

(Production Method 1) Of the compounds of the present invention represented by the general formula 3,^ThreeIs N
R^4-1R^5-1(R^4-1, R ^5-1Are C1-C4 alkyl, respectively.
, A C2-C5 alkoxyalkyl group, a C3-C4
Lucanoyloxyalkyl group or C (= O) R⁶(R⁶Is
C1-C4 alkyl group, C1-C4 haloalkyl group, C
2-C4 alkoxyalkyl group, C2-C4 alkoxy
Carbonyl group or C3-C4 alkanoyloxyalkyl
Represents a hydroxyl group. ). )) The compound of the present invention represented by the general formula^ThreeIs N
R^4-1R^5-1Is a compound of the general formula

Embedded image (Wherein, R ¹ , R ² , m and n have the same meanings as described above;
^4-1 C1-C4 alkyl group, C2-C5 alkoxyalkyl group, C3-C4 alkanoyloxy group or a ^{C (= O) R 6 (} R 6 is C1-C4 alkyl group, C1-
C4 haloalkyl group, C2-C4 alkoxyalkyl group, C2-C4 alkoxycarbonyl group or C3-C4
Represents an alkanoyloxyalkyl group. ). ) And an amine compound represented by the general formula

^Embedded image wherein R ^5-1 is a C1-C4 alkyl group, a C2-C5 alkoxyalkyl group, a C3-C4 alkanoyloxyalkyl group or C (） O) R ⁶ (R ⁶ is C1-C4 alkyl group, C1-C4 haloalkyl group, C2-C4 alkoxyalkyl group, C2-C4 alkoxycarbonyl group or C
Represents a 3-C4 alkanoyloxyalkyl group. ). Z is such that R ^5-1 is a C1-C4 alkyl group, C2-C5
When it is an alkoxyalkyl group or a C3-C4 alkanoyloxyalkyl group, it represents a halogen atom;
^{When 5-1} is C (＝ O) R ⁶ , it represents a halogen atom or an OC (＝ O) R ⁶ group. ) To react with the compound represented by the formula (1). The reaction is usually performed in a solvent in the presence of a base. Examples of the base used in the reaction include inorganic bases such as potassium carbonate and sodium hydride, and organic bases such as triethylamine, diisopropylethylamine and pyridine.

In the reaction, a solvent inert to the reaction can be used. Specifically, for example, 1,4-dioxane,
Ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl ether and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether; aromatic hydrocarbons such as toluene and xylene; And acid amides such as N-dimethylformamide and mixtures thereof. The amount of the compound represented by the general formula (6) used in the reaction can achieve the purpose at a ratio of 1 mol to 1 mol of the compound represented by the general formula (5), but is changed depending on the reaction situation. be able to. The amount of the base used in the reaction is 1 mole per 1 mole of the compound represented by the general formula (5).
The purpose can be achieved in molar proportions, but can be varied depending on the circumstances of the reaction. The reaction temperature range is
Usually, it is in the range of −30 to 120 ° C. The range of the reaction time is usually 0.1 to 100 hours. After the reaction, the compound of the present invention can be obtained, for example, by performing the following post-treatment. 1. The reaction solution was poured into water, extracted with an organic solvent, and then concentrated.
If necessary, purification operations such as chromatography and recrystallization are further performed. 2. The reaction solution is concentrated as it is, and if necessary, purification operations such as chromatography and recrystallization are performed.

(Production method 2) A method for producing the compound represented by the general formula 5 is a compound represented by the general formula 5

Embedded image (In the formula, R ¹ , R ² , m, and n represent the same meaning as described above.)
And a compound represented by the general formula

^Embedded image R ^4-1 Z (wherein, R ^4-1 is a C1-C4 alkyl group, a C2-C5 alkoxyalkyl group, a C3-C4 alkanoyloxyalkyl group, or C (＝ O) R ⁶ (R ⁶ is C1-C4 alkyl group, C1-C4 haloalkyl group, C2-C4 alkoxyalkyl group, C2-C4 alkoxycarbonyl group or C
Represents a 3-C4 alkanoyloxyalkyl group. ). Z is a group in which R ^4-1 is a C1-C4 alkyl group, C2-C5
When it is an alkoxyalkyl group or a C3-C4 alkanoyloxyalkyl group, it represents a halogen atom;
When R ^4-1 is a C (＝ O) R ⁶ group, it represents a halogen atom or an OC (＝ O) R ⁶ group. ) To react with the compound represented by the formula (1). The reaction is usually performed in a solvent in the presence of a base. Examples of the base used in the reaction include inorganic bases such as potassium carbonate and sodium hydride and organic bases such as triethylamine, diisopropylethylamine and pyridine.

In the reaction, a solvent inert to the reaction can be used. Specifically, for example, 1,4-dioxane,
Ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl ether and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether; aromatic hydrocarbons such as toluene and xylene; And acid amides such as N-dimethylformamide and mixtures thereof. The amount of the compound represented by the general formula (1) used in the reaction may be 1 mol per 1 mol of the compound represented by the general formula (1), but is within a range in which the target compound can be obtained. Can change. The amount of the base used in the reaction can achieve the target at a ratio of 1 mole to 1 mole of the compound represented by the general formula 7, but can be changed within a range where the target product can be obtained. The range of the reaction temperature is usually from -30 to 120C. The range of the reaction time is usually 0.1 to 100 hours. After the reaction, the compound of the present invention can be obtained, for example, by performing the following post-treatment. 1. The reaction solution was poured into water, extracted with an organic solvent, and then concentrated.
If necessary, a purification operation such as chromatography and recrystallization. 2. A method in which the reaction solution is directly concentrated and, if necessary, further subjected to purification operations such as chromatography and recrystallization. When the compound represented by the general formula (5) is used as the starting compound of the above (Production method 1), the product is not isolated and the reaction of the (Production method 2) is followed by the production method (Production method 1). Can also be carried out.

(Production Method 3) Among the compounds of the present invention, a method for producing a compound represented by the following general formula:

Embedded image (In the formula, R ¹ , R ² , m, and n represent the same meaning as described above.)
By subjecting a nitropyridine compound represented by the following formula to a reduction reaction. The reduction reaction can be performed, for example, by the following (Production method 3-1) and (Production method 3-2).

(Production Method 3-1) A method of subjecting the compound represented by the general formula (9) to a reduction reaction using a simple metal or a metal halide in the presence of acidic water. Done in Acidic water used for the reduction reaction includes, for example, hydrochloric acid, aqueous sulfuric acid, and aqueous acetic acid, and simple metals or metal halides include, for example, zinc, tin, iron, and stannous chloride. As a solvent that can be used for the reduction reaction,
For example, alcohols such as methanol, ethanol and propanol, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl ether, te
Ethers such as rt-butyl methyl ether, esters such as ethyl acetate and methyl propionate, and mixtures thereof can be used.

The amount of acidic water used in the reduction reaction can vary depending on the reaction conditions, but is usually an excess amount, and the amount of a simple metal or a metal halide is usually
3 to 10 based on 1 mol of the compound represented by the general formula
It is a mole ratio. The range of the reduction reaction temperature is usually from 0 to
It is in the range of 150 ° C. The range of the reaction time is usually 0.1.
5 to 100 hours. After the reaction, the compound of the present invention can be obtained by performing the following post-treatment operations. 1. The reaction solution is poured into water, and a base (for example, aqueous ammonia) is added.
The solution is neutralized with, filtered, and the filtrate is extracted with an organic solvent and concentrated.
Further, if necessary, purification operations such as chromatography and recrystallization are performed. 2. The reaction solution is poured into water, extracted with an organic solvent and concentrated. If necessary, purification operations such as chromatography and recrystallization are further performed.

(Production method 3-2) A compound represented by the following general formula (9) was prepared in the presence of a transition metal catalyst.
Method of subjecting to reduction reaction with hydrogen The reduction reaction is usually performed in a solvent. Examples of the transition metal catalyst used for the reduction reaction include Pd / C, Pd
/ SrCO ₃ , PtO ₂ and Raney nickel.

In the reaction, a solvent inert to the reaction can be used, and specific examples thereof include alcohols such as methanol, ethanol and propanol, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. , Diethyl ether, tert-butyl methyl ether and the like; esters such as ethyl acetate and methyl propionate; fatty acids such as acetic acid and propionic acid; and mixtures thereof. The amount of the transition metal catalyst used in the reduction reaction is usually 0.001 to 0.2 mol based on 1 mol of the compound represented by the general formula (9).
Usually, the amount of hydrogen can achieve the purpose at a ratio of 3 moles per mole of the compound represented by the general formula (9). The reaction temperature is usually in the range of 0 to 150 ° C. The range of the reaction time is usually 0.5 to 100 hours. After the reaction, the compound of the present invention can be obtained by performing the following post-treatment operations. 1. The reaction is filtered and the filtrate is concentrated. Further, if necessary, purification operations such as chromatography and recrystallization are performed. 2. The reaction solution is poured into water, extracted with an organic solvent and concentrated. If necessary, purification operations such as chromatography and recrystallization are further performed.

[0020] Among the compounds represented by (Process 4) Formula of 3, Among the compounds of the present invention represented by the manufacturing method Formula of 3 and R ³ is a hydrogen atom, R ³ is a hydrogen atom Is obtained by adding a compound represented by the general formula (7) to a compound represented by the general formula (7) in the presence of ethers (for example, tetrahydrofuran, diethyl ether, 1,4-dioxane and ethylene glycol dimethyl ether).

Embedded image The compound can be produced by reacting a nitrite represented by R ⁹ ONO ₂ (wherein R ⁹ represents a C1-C5 alkyl group). The reaction is performed without a solvent or in a solvent. Examples of nitrites that can be used for the reaction include isoamyl nitrite, isobutyl nitrite, and t-butyl nitrite. The reaction can be carried out using ethers in a solvent amount, and it is also possible to use a solvent inert to the reaction.

The amount of the nitrite used in the reaction can achieve the purpose at a ratio of 1 mol to 1 mol of the compound represented by the general formula (7), but may vary depending on the reaction conditions. Can be. The reaction temperature is usually in the range of 0 to 150 ° C. The range of the reaction time is usually 0.5 to 100 hours. After the reaction, the compound of the present invention can be obtained by performing the following post-treatment operations. 1. The reaction solution is concentrated as it is. If necessary,
Further, purification operations such as chromatography and recrystallization are performed. 2. The reaction solution is poured into water, extracted with an organic solvent, and then concentrated. If necessary, purification operations such as chromatography and recrystallization are further performed.

(Production Method 5) Of the compounds of the present invention represented by the general formula 3, R ³ is N
ＣＲCR ⁷ R ⁸ (where R ⁷ represents a hydrogen atom or a C1-C4 alkyl group, and R ⁸ represents a C1-C4 alkoxy group) Among the compounds of the present invention represented by general formula 3, R ³ is N
ＣＲCR ⁷ R ⁸ (R ⁷ represents a hydrogen atom or a C1-C4 alkyl group, and R ⁸ represents a C1-C4 alkoxy group) is a compound represented by the following general formula:
1

Wherein CR ⁷ (OR ¹⁰ ) ₃ wherein R ⁷ is a hydrogen atom or a C1-C4 alkyl group;
¹⁰ represents a C1-C4 alkyl group. The reaction can be carried out by reacting an orthoester compound represented by the formula (1). The reaction is carried out in the presence or absence of an acid, without a solvent or in a solvent.

The orthoesters usable in the reaction include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoformate, ethyl orthopropionate, methyl orthobutyrate and methyl orthovalerate Is mentioned. Examples of the acid used for the reaction include inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as acetic acid and p-toluenesulfonic acid.
The reaction can be carried out using an orthoester compound in a solvent amount, or can be carried out in a solvent inert to the reaction. As the solvent inert to the reaction in this case, for example,
Ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl ether, tert-butyl methyl ether, aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, and aromatics such as toluene and xylene Group hydrocarbons and mixtures thereof can be used.

The amount of the orthoester compound used in the reaction is 1 to 1 mol of the compound represented by the general formula (7).
Molar to excess. The reaction temperature range is usually from 0 to 1
It is in the range of 50 ° C. The range of the reaction time is usually 0.5
~ 100 hours. After the reaction, the compound of the present invention can be obtained by performing the following post-treatment operations. 1. The reaction solution is concentrated as it is. If necessary,
Further, purification operations such as chromatography and recrystallization are performed. 2. The reaction solution is poured into water, extracted with an organic solvent, and then concentrated. If necessary, purification operations such as chromatography and recrystallization are further performed.

(Production Method 6) Of the compounds of the present invention represented by the general formula 3, R ³ is N
ＣＲCR ⁷ R ⁸ (R ⁷ represents a hydrogen atom or a C1-C4 alkyl group, and R ⁸ represents a phenyl group which may be substituted)
Production Method of the Compound of the Present Invention Among the compounds of the present invention represented by the general formula 3, R ³ is N
ＣＲCR ⁷ R ⁸ (R ⁷ represents a hydrogen atom or a C1-C4 alkyl group, and R ⁸ represents a phenyl group which may be substituted)
The compound represented by the general formula is a compound represented by the general formula

Embedded image (In the formula, R ⁷ represents a hydrogen atom or a C1-C4 alkyl group, and R ¹¹ represents a phenyl group which may be substituted.)
And a carbonyl compound represented by the following formula: The reaction is performed without solvent or in an inert solvent. The amount of the carbonyl compound represented by the general formula 12 used in the reaction is 1 to a large excess with respect to 1 mol of the compound represented by the general formula 7, and the carbonyl compound represented by the general formula 12 is used. It is also possible to use as a solvent. The reaction temperature is usually from 0 to 15
Within the range of 0 ° C. The reaction time is usually 0.5 to 10
0 hours. After the reaction, the compound of the present invention can be obtained by performing the following post-treatment operations. 1. The reaction solution is concentrated as it is. If necessary,
Further, purification operations such as chromatography and recrystallization are performed. 2. Water is poured into the reaction solution, and the mixture is extracted with an organic solvent and concentrated. If necessary, purification operations such as chromatography and recrystallization are further performed. 3. The reaction solution is cooled, and the precipitated crystals are collected by filtration. Also,
If necessary, purification operations such as chromatography and recrystallization are further performed.

Next, a method for producing a compound represented by the general formula 9 which is an intermediate of the compound of the present invention will be described. The compound represented by the general formula 9 is 2,4-dichloro-3-
Nitropyridine and general formula

Embedded image (Wherein R ² and n represent the same meaning as described above) with a phenol compound represented by the following general formula:

Embedded image (Wherein R ² and n represent the same meaning as described above) (first step), and then a compound represented by the general formula
And a compound represented by the general formula

Embedded image (Wherein, R ¹ and m represent the same meaning as described above) in the presence of a base (second step).

First, the first step will be described. The reaction is usually performed in a solvent in the presence of a base. Examples of the base used in the reaction include inorganic bases such as potassium carbonate and sodium hydride and organic bases such as triethylamine, diisopropylethylamine and pyridine. In the reaction, a solvent inert to the reaction can be used, and specifically, for example, ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl ether, and tert-butyl methyl ether ,
Aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, aromatic hydrocarbons such as toluene and xylene, N, N-dimethylformamide, and mixtures thereof can be used. General formula used for the reaction
The amount of the phenol compound represented by Chemical formula 13 can achieve the purpose at a ratio of 1 mol to 1 mol of 2,4-dichloro-3-nitropyridine, but can be changed according to the reaction situation. . The reaction temperature range is usually from 0 to
It is in the range of 150 ° C. The range of the reaction time is usually 0.1.
5 to 100 hours. The amount of the base used in the reaction is
The purpose can be sufficiently achieved at a ratio of 1 mol to 1 mol of the phenol compound represented by the general formula (13), but can be changed according to the reaction situation. After the reaction, the reaction solution is poured into water, subjected to a usual post-treatment such as concentration after extraction with an organic solvent, and, if necessary, further purification by chromatography, recrystallization, etc. The compound represented by Formula 14 can be isolated. Further, the reaction solution containing the compound represented by the general formula (14) can be used in the second step without performing a post-treatment operation.

Next, the second step will be described. The reaction is usually performed in a solvent in the presence of a base. Examples of the base used in the reaction include inorganic bases such as potassium carbonate and sodium hydride, and organic bases such as triethylamine, diisopropylethylamine and pyridine.

In the reaction, a solvent inert to the reaction can be used. Specifically, for example, 1,4-dioxane,
Ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl ether and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether; aromatic hydrocarbons such as toluene and xylene; , N-dimethylformamide and the like and mixtures thereof can be used. The amount of the phenolic compound represented by the general formula (1) used in the reaction can achieve the purpose at a ratio of 1 mol per 1 mol of the compound represented by the general formula (14), but varies depending on the reaction situation. can do. The amount of the base used in the reaction is
The purpose can be achieved at a ratio of 1 mole to 1 mole of the phenol compound represented by the general formula (15), but can be changed according to the reaction situation. The reaction temperature is usually in the range of 0 to 150 ° C. The range of the reaction time is usually 0.5 to 100 hours. After the reaction, the reaction solution is poured into water, subjected to a usual post-treatment such as concentration after extraction with an organic solvent, and, if necessary, chromatography, recrystallization and other purification operations. A compound represented by Formula 9 can be obtained.

The starting material, 2,4-dichloro-3-nitropyridine, is described, for example, in International Patent Publication WO99 / 4409.
It can be produced by the method described in Japanese Patent Publication No.

The arthropod pest control agent of the present invention can be used as it is, but is usually formulated and used. As the preparation, for example, granules, powder,
Solid preparations such as wettable powders and liquid preparations such as oil preparations, emulsions, flowable preparations, microcapsules and the like can be mentioned. The arthropod pest control agent of the present invention contains the compound of the present invention as an active ingredient in an amount of usually 0.01% to 95% by weight percentage depending on the preparation.
contains. The arthropod pest control agent of the present invention can be obtained by mixing a compound of the present invention with a carrier, a surfactant, a fixing agent, a thickener, a stabilizer, and the like, followed by pulverization and processing. Examples of the carrier used in such formulation include solid carriers such as clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fusami clay, acid clay, etc.), talc, ceramics, and other inorganic minerals (cellulose). Site, quartz, activated carbon, calcium carbonate, hydrated silica,
Montmorillonite, etc.), liquid carriers, water, alcohols (methanol, ethanol, ethylene glycol, propylene glycol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene) , Methyl naphthalene,
Phenylxylylethane, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, gas oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl Ethers, dioxane, etc.), acid amides (N,
N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil, etc., and gaseous carrier {fluorocarbon gas, Butane gas, LPG (liquefied petroleum gas),
Dimethyl ether, carbon dioxide, etc., and examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, polyoxyethylenated alkyl aryl ethers, and polyethylene. Glycol ethers, polyhydric alcohol esters, sugar esters, and sugar alcohol derivatives are mentioned. Examples of the fixing agent include casein, gelatin, polysaccharides (starch, gum arabic, xanthan gum, cellulose derivatives, alginic acid, etc.), Examples include lignin derivatives, bentonite, saccharides, and synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, and the like). Examples of thickeners include polysaccharides (xanthan gum and the like) and inorganic minerals (aluminum). Beam magnesium silicate, etc.), and examples of the stabilizer, for example, PAP (acidic isopropyl phosphate), BHT (2,6-di -tert- butyl-4-methylphenol - Le), BHA (2-tert
A mixture of butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids, and fatty acid esters.

Examples of the method of using the preparation of the arthropod pest control agent of the present invention include the following methods, which can be appropriately selected according to the dosage form of the preparation, the place of use, and the like. 1. A method of treating the preparation as it is in the habitat of the pest. 2. A method in which a preparation is diluted with a solvent such as water and then treated at a place where a pest inhabits. 3. A method in which a preparation is heated in a habitat of a pest to volatilize an active ingredient.

The arthropod pest control agent of the present invention can be mixed with or used in combination with other insecticides, nematicides, acaricides, and the like. Examples of the active ingredients of the insecticide, acaricide and nematicide which can be used in combination or in combination include, for example, fenitrothion, fenthion, diazinon, chlorpyrifos, acephate, metidathion, disulfoton, DDVP, sulfophos, profenophos, cyanophos, dioxa. Benzofos, dimethoate, phentoate, malathion, trichlorfon, azinphosmethyl, monocrotophos, ethion, phosthiazate and other organic phosphorus compounds, BPMC, benflacarb, propoxur, carbosulfan, carbofuran, carbaryl,
Carbamate compounds such as mesomil, ethiophenecarb, aldicarb, oxamyl, phenothiocarb, thiodicarb, and alanicarb;

Etofenprox, halfenprox, fenvalerate, esfenvalerate, fenpropatrin, cypermethrin, alpha cypermethrin, zetacypermethrin, permethrin, cyhalothrin, lambda cyhalothrin, deltamethrin, cycloprothrin, taufulvari Pyrethroid compounds such as catenate, flucitrinate, bifenthrin, acrinathrin, cyfluthrin, β-cyfluthrin, tralomethrin, and silafluofen;

Neonicotinoid compounds such as acetamiprid, thiamethoxam and nitenpyram, thiadiazine derivatives such as buprofezin, cartap, thiocyclam,
Nereistoxin derivatives such as bensultap, endosulfan, chlorinated hydrocarbon compounds such as γ-BHC, chlorfluazuron, teflubenzuron, flufenoxuron, hexaflumuron, benzoylphenylurea compounds such as lufenuron, amitraz, chlordimeform and the like Formamidine derivatives, phenylpyrazole-based compounds, tebufenozide, methoxyphenozide, halofenozide, phenylphenazine derivatives such as chromafenozide, chlorfenapyr, bromopropylate, propargite, fenbutatin oxide, hexthiazox, clofenthedine, ethoxyxazole, acequinosyl, biphenazepate, pyrifenazate, pyrifenazepate Fentiuron, tebufenpyrad, pyrimidifen, fenazaquin, poly Kuching complex [Tetoranakuchin, Jinakuchin, Torinakuchin], milbemectin,
Evermectin, emamectin benzoate, azadirachtin, pymetrozine, indoxacarb, spinosyn derivatives and the like.

Examples of arthropod pests that can be controlled by the arthropod pest control agent of the present invention include harmful insects and harmful mites, and specific examples include the following. Hemiptera: Insects and Planthoppers (Laodelphax)
striatellus), brown planthopper (Nilaparvata lugen)
s), stag beetle (Sogatella furcifera), etc., leafhoppers, and black leafhopper (Nephotettix cincticep)
s), Leafhopper (Nephotettix viresc)
ens), aphids, cotton aphids (Aphis go
ssypii), peach aphid (Myzus persicae),
Citrus aphid (Aphis citricola), radish aphid (Lipaphis pserudobrassicae), Papilio aphid (Nippolachnus piri), Citrus aphid (Toxoptera aurantii), Citrus aphid (Toxoptera ciidius), etc. Nezara antennata), Coleus punctiger, Coleoptera (R)
iptortus clavetus, Baba stink bug (Plauti)
astali), whitefly, whitefly (Trialeurodes vaporariorum), tobacco whitefly (Bemisia tabaci), silver leaf whitefly (Bem)
isia argentifolii), scale insects (Aonidiella aurantii), San Jose scale scale (Comstockaspis perniciosa), citrus snow scale (Unaspis citri), scale scale scale (Pseudaulacaspis pentagona), olive scale scale (Saissetia ole) Oyster scales (Lepidosaphes beckii), Ruby beetle (Ce)
roplastes rubens, Icerya scale insect (Icerya)
purchasi), worms, lice, etc.

Lepidopteran insect pests: the phytoceranidae (Chil)
o suppressalis, Coleoptera (Cnaphalocrocis m)
edinalis, European Corn Borer (Ostrinia)
nubilalis, Shibattoga (Parapediasia teterrell)
a), Notarchaderogata, Plodia interpunctella, etc., Noctuids {Spodoptera litura), Armyworm (Ps)
eudaletia separata, armyworm (Mamestra brassic)
ae), Agrotis ipsilon, Trichoplastia, Heliotis, Helicoverpa, etc., White butterfly (Pieris rapae), etc., Peripheries (Adoxophyes), Nasihimesugi (Grapho)
lita molesta), codling moth (Cydia pomonella)
｝, イ ガ ｛｛Car (Carposina nip
onensis), etc .;
Dokuga (Limantria, Euproctis, etc.),
Suga (Plutella xylostella, etc.), Kibaga (Pectinophora gossypiella)
｝, Triggers ｛, Hyphantriacu
nea), etc., Hirozuga moth, iga (Tinea translucen)
s), carp (Tineolabisselliella), etc.

Diptera pests: Culex mosquitoes (Cule)
x pipiens pallens) and Culex pipiens (Culex tr)
itaeniorhynchus), Aedes aegypt
i), (Aedes albopictus), etc., Anopheles sinensis, etc., chironomids, house flies, house flies (Musca domestica), house flies (Muscina stabulans), etc., blowflies, flies, and flies (Delia platura), flies (onion fly (Delia antiqua), etc.), fruit flies, drosophila, fly flies, black flies, flies, sand flies, flies, etc.

Coleoptera: Scarabaeids: Scarabaeids (Anomala cuprea), Scutellaria (Anomala rufo)
cuprea), weevil, maize weeville (Sitoph)
ilus zeamais, rice weevil (Lissorhoptrus)
oryzophilus), alfalfa weevil (Hypera)
pastica), Callosobruchuys chie
nensis), etc., Tenebrion beetles, Tenebriomolitor, Tenebriomolitor (T)
ribolium castaneum), beetle, turtle beetle (Au
lacophora femoralis) and the flea beetle (Phyllotre)
ta striolata), Colorado potato beetle (Leptinotarsa dec)
emlineata), Western Corn Loom (Diabrot)
ica virgifera virgifera), Southern corn root worm (Diabrotica undecimpunctata howardi), etc.
Shiban beetles, epilacunas (Epilachna vigintioctopunctata, etc.), giant leaf beetles, Nagasin beetles, longhorn beetles, Paederus fuscipes, and the like.

Cockroach pests: German cockroaches (Blat
tella germanica), black cockroach (Periplaneta ful)
iginosa), American cockroach (Periplaneta american)
a), a brown cockroach (Periplaneta brunnea), a brown cockroach (Blatta orientalis) and the like. Thrips pests: Thrips palmi (Thrips
palmi), Thrips tabaci, Thrips thrips (Thrips hawaiiensis), Thrips thrips (Scirtothrips dorsalis), Thrips thrips (Frankliniella intonsa), Citrus thrips (Frankliniella occalis, etc.) Hymenoptera pests: ants, hornets, wasps,
Japanese wasps (Athalia japonica)
And so on.

Orthoptera pests: Kera, grasshoppers and the like. Laminaria pests: cat flea (Ctenocephalides felis), dog flea (Ctenocephalides canis), and human flea (Pulex i
rritans). Louse pests: White lice (Pediculus humanus co)
rporis), psyllium (Phthirus pubis) and the like. Termite pests: Reticulitermes sp.
eratus), House termite (Coptotermes formosanus)
etc. Acarid pests: spider mites ｛Tetranychus urt
icae), Kanzawa spider mite (Tetranychus kanzawai),
Citrus spider mite (Panonychus citri), apple spider mite (P
anonychus ulmi), etc., Spider mites (genus Brevipalpus, etc.) and dust mites {Polyphagotar
sonemus latus), Fushi mite, Rutani (Aculopus pelekassi), Crabcarus (Calacarus)
carinatus), ticks and ticks (Hae)
maphyxalis longicornis, Bovine tick (Boophilus)
microplus), etc., acarid mites, and acarid mites (Tyr
ophagus putrescentiae), Dermatophagoides mite (Dermatophagoides farinae), Dermatophagoides ptrenyssnus, etc.
letus malaccensis) and southern mites (Cheyletus moo
rei) etc., mites and the like. Furthermore, the arthropod pest control agent of the present invention is also effective for pests that have developed resistance to the existing arthropod pest control agents.

[0042]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples, and Test Examples, but the present invention is not limited to these Examples. First, Production Examples of the compound of the present invention will be shown. The number of the compound of the present invention is shown in Table 1 below.
It is the compound number described in Table 2.

Production Example 1 [3-Amino-2,4-di (4-
Fluoro-3-trifluoromethylphenoxy) pyridine (method for producing compound (1) of the present invention) (First step) 2,4-dichloro-3-nitropyridine (0.39 g, 2 mmol) and 4-fluoro- 3-
Trifluoromethylphenol (0.72 g, 4 mmol) was dissolved in N, N-dimethylformamide (20 ml), potassium carbonate (0.61 g, 4.4 mmol) was added, and the mixture was stirred at room temperature for 12 hours. Thereafter, the reaction mixture was poured into water and extracted with ethyl acetate. The organic phase was washed with saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 2,4-di (4-fluoro-3-trifluoromethylphenoxy) -3-nitropyridine. ¹ H-NMR (250 MHz; CDCl ₃ / TMS): δ
(Ppm) 8.06 (d; J = 5.8 Hz, 1H), 7.
53-7.22 (m, 6H), 6.50 (d; J = 5.8
Hz, 1H)

(Second Step) The 2, obtained in the first step,
4-Di (4-fluoro-3-trifluoromethylphenoxy) -3-nitropyridine is converted into diethyl ether (2 m
l), and stannous chloride dihydrate (4.
(5 g, 20 mmol) in concentrated hydrochloric acid (20 ml) was added at room temperature. After the addition, the mixture was stirred at room temperature for 12 hours. Thereafter, the reaction mixture was poured into water, cooled to 0 ° C., and neutralized with aqueous ammonia. Ethyl acetate was added thereto, and insolubles were removed by filtration through celite, followed by liquid separation. The organic phase was washed with brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was subjected to silica gel chromatography to give 3-amino-2,4-
0.34 g of di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (1)) was obtained. 83.9 ° C. ¹ H-NMR (300 MHz; CDCl ₃ / TMS) δ
(Ppm): 7.46 (d; J = 5.7 Hz, 1H),
7.45-7.20 (m, 6H), 6.42 (d; J = 5.
7 Hz, 1H), 4.06 (br.s, 2H) Production Example 2 [2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the production method of the present compound (2)]] 3 -Amino-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (0.23 g, 0.51)
Mmol) in tetrahydrofuran (5 ml),
At 50-60 ° C, t-butyl nitrite (58 mg, 0.5
(6 mmol) in tetrahydrofuran (0.5 ml) was added dropwise over 20 minutes. After the addition was completed, the mixture was heated under reflux for 3 hours. Thereafter, the reaction solution was cooled, concentrated under reduced pressure, and the obtained residue was subjected to silica gel chromatography to give 2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the compound of the present invention (2 ))
0.11 g was obtained. mp 66.4 ° C. ¹ H-NMR (300 MHz; CDCl ₃ / TMS) δ
(Ppm): 8.04 (d; J = 5.7 Hz, 1H),
7.45-7.19 (m, 6H), 6.63 (dd; J =
5.7, 1.8 Hz, 1H), 6.41 (d; J = 1.8H)
z, 1H)

Production Example 3 [3-acetamido-2,4-di (4-fluoro-3-trifluoromethylphenoxy)
Pyridine (the present compound (5)) and 3-diacetylamino-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (11))
Production method of 3-amino-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (0.25 g, 0.5
(5 mmol) was dissolved in toluene (5 ml), and acetic anhydride (0.15 g, 1.47 mmol) and pyridine (0.16 g, 2.0 mmol) were added dropwise under ice cooling. afterwards,
The mixture is left at room temperature for 12 hours and
Stirred for hours. After cooling the reaction solution to room temperature, it was poured into water,
Extracted with ethyl acetate. Wash the organic phase with saturated saline,
After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 3-diacetylamino-2,4-di (4-
93 mg of fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (11)) and 3-acetamido-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (5)) 1
20 mg were obtained.

3-Diacetylamino-2,4-di (4-
Fluoro-3-trifluoromethylphenoxy) pyridine m. p. 113.0 ° C. ¹ H-NMR (250 MHz; CDCl ₃ / TMS) δ
(Ppm): 8.04 (d; J = 5.8 Hz, 1H),
7.41-7.20 (m, 6H), 6.48 (d; J =
5.8Hz, 1H), 2.45 (s, 6H)

3-acetamido-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine m. p. 153.8 ° C. ¹ H-NMR (300 MHz; CDCl ₃ / TMS) δ
(Ppm): 7.88 (d; J = 5.7 Hz, 1H),
7.54-7.02 (m, 6H), 6.43 (d; J =
5.7 Hz, 1H), 2.84 (br.s, 1H),
2.22 (s, 3H)

Production Example 4 [Method for producing 3-trifluoroacetamido-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (compound (7) of the present invention] 3-amino-2,4 -Di (4-fluoro-3-trifluoromethylphenoxy) pyridine (0.18 g, 0.4
) Was dissolved in toluene (5 ml), pyridine (32 mg, 0.4 mmol) was added, and then trifluoroacetic anhydride (84 mg, 0.4 mmol) was added dropwise under ice cooling. Thereafter, the mixture was stirred at room temperature for 12 hours. The residue obtained by directly concentrating the reaction solution under reduced pressure was subjected to silica gel column chromatography to give 3-trifluoroacetamide-2,4-di (4-fluoro-
0.18 g of (3-trifluoromethylphenoxy) pyridine (the present compound (7)) was obtained. m. p. 126.1 ° C. ¹ H-NMR (300 MHz; CDCl ₃ / TMS) δ
(Ppm): 7.97 (d; J = 5.7 Hz, 1H),
7.92 (br.s; 1H), 7.48-7.22
(M, 6H), 6.45 (d; J = 5.7 Hz, 1H)

Production Example 5 [Method for producing 3- (N-acetyl-N-butyrylamino) -2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (Compound (15) of the present invention] (5) 0.30 g and pyridine 0.059 ml
Was dissolved in 10 ml of toluene, and 0.070 ml of butyryl chloride was added with stirring at room temperature. After stirring at room temperature for 3 hours, the mixture was heated under reflux for 12 hours. After returning the reaction solution to room temperature, 10% hydrochloric acid was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid, a saturated saline solution and a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 3- (N-acetyl-
N-butyrylamino) -2,4-di (4-fluoro-3
0.24 g of (-trifluoromethylphenoxy) pyridine (the present compound (15)) was obtained. Yield 70% n _D ^24.5 1.4951

Production Example 6 [3- (N-ethoxymethyleneamino) -2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (compound of the present invention (4
Production method of 1))] 0.20 g of compound (1) was added to 5 ml of triethyl orthoformate.
And heated and stirred at 70-80 ° C. for 6 hours. The reaction solution was concentrated under reduced pressure, and the obtained crystals were recrystallized from a mixture of hexane: ethyl acetate = 10: 1 to give 3- (N-ethoxymethyleneamino) -2,4-di (4-fluoro- 3-
0.10 g of (trifluoromethylphenoxy) pyridine (the present compound (41)) was obtained. Yield 45% mp 135.4 ° C

Production Example 7 [2,4-di (4-fluoro-
3-trifluoromethylphenoxy) -3- (N-methoxymethyleneamino) pyridine (the compound of the present invention (4
2)) Production method] 0.20 g of compound (1) was added to 5 ml of trimethyl orthoformate.
And heated and stirred at 70-80 ° C. for 6 hours. The reaction solution was concentrated under reduced pressure, and the obtained crystals were washed with hexane.
0.16 g of 2,4-di (4-fluoro-3-trifluoromethylphenoxy) -3- (N-methoxymethyleneamino) pyridine (the present compound (42)) was obtained. Yield 74% mp 129.2 ° C

Production Example 8 [3- (N-ethylamino)-
2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (43)) and 3
Method for producing-(N, N-diethylamino) -2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (Compound (44) of the present invention) 0.30 g of compound (1) was added to N, N -Dissolved in 3 ml of dimethylformamide, added 0.092 g of potassium carbonate,
While stirring at room temperature, 0.053 ml of iodoethane was added dropwise. After stirring at room temperature for 9 hours, the mixture was stirred at 60 ° C. for 4 hours. Thereafter, 0.1 ml of iodoethane was added, and the mixture was stirred at 60 ° C. for 1 hour.
Stirred at C for 1 hour. Furthermore, iodoethane 0.1ml
And 0.1 g of potassium carbonate, and the mixture was stirred at 60 ° C. for 1 hour. The reaction solution was returned to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated saline solution, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 3- (N-ethylamino) -2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (43)
0.020 g (yield 6%, ¹ H-NMR (CDCl ₃ , T
MS, δ (ppm): 1.23 (3H, t), 3.43
(2H, br.q), 3.93 (1H, br.s),
6.44 (1H, d), 7.19 to 7.43 (6H,
m), 7.49 (1H, d)) and 3- (N, N-diethylamino) -2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (44)) 0 .17 g (50% yield, n _D ^24.5 1.
5079).

Production Example 9 [3-Amino-2,4-di (4-
Chloro-3-trifluoromethylphenoxy) pyridine (a method for producing the compound (45) of the present invention)] 4-chloro-3-trifluoromethylphenol is used in place of 4-fluoro-3-trifluoromethylphenol in Production Example 1. Except for using 3-amino-2,
4-Di (4-chloro-3-trifluoromethylphenoxy) pyridine (the present compound (45)) was obtained. mp 100.5 ° C. ¹ H-NMR (300 MHz; CDCl ₃ / TMS) δ
(Ppm): 7.57-7.43 (m, 5H), 7.33
(Dd; J = 8.7 Hz, J = 2.7 Hz, 1H), 7.20
(Dd; J = 8.8 Hz, J = 2.8 Hz, 1H), 6.49
(D; J = 5.5 Hz, 1H), 4.06 (br.s, 2
H)

Production Example 10 [3-Amino-2,4-di (4
-Bromo-3-trifluoromethylphenoxy) pyridine (Method for producing compound (46) of the present invention)] Instead of 4-fluoro-3-trifluoromethylphenol in Production Example 1, 4-bromo-3-trifluoromethylphenol Except that 3-amino-2,
4-Di (4-bromo-3-trifluoromethylphenoxy) pyridine (the present compound (46)) was obtained. mp 109.6 ° C. ¹ H-NMR (250 MHz; CDCl ₃ / TMS) δ
(Ppm): 7.72 (d; J = 8.7 Hz, 1H),
7.58-7.43 (m, 4H), 7.26 (dd; J =
7.9 Hz, J = 3.3 Hz, 1 H), 7.12 (dd; J =
7.7 Hz, J = 2.6 Hz, 1H), 6.49 (d; J = 5.
6Hz, 1H), 4.06 (br.s, 2H)

Production Example 11 [3-acetoxyacetamide-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (a method for producing the compound (47) of the present invention)] 3-amino-2,4- Di (4-fluoro-3-trifluoromethylphenoxy) pyridine (0.20 g, 0.4
4 mmol) in toluene (5 ml), triethylamine (45 mg, 0.45 mmol) was added, and then acetoxyacetic chloride (54 mg, 0.3 mg) was added under ice-cooling.
9 mmol) was added dropwise. The mixture was stirred at room temperature for 12 hours. Thereafter, the reaction solution was concentrated under reduced pressure as it was,
The obtained residue was subjected to silica gel column chromatography to give 3-acetoxyacetamide-2,4-di (4
0.16 g of (fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (47)) was obtained. ^{m.p. 101.8 ℃ 1 H-NMR (} 300MHz; CDCl 3 / TMS) δ
(Ppm): 7.92 (d; J = 5.7 Hz, 1H),
7.51-7.20 (m, 6H), 6.45 (d; J =
5.7 Hz, 1H), 4.77 (s, 2H), 2.22
(S, 3H)

Production Example 12 [3-Methoxyacetamide-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (Production Method of Compound (48) of the Present Invention)] In the same manner except that methoxyacetic acid chloride was used instead, 3-methoxyacetamido-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (48)) pyridine was obtained. mp 120.0 ° C. ¹ H-NMR (300 MHz; CDCl ₃ / TMS) δ
(Ppm): 7.96 (br.s, 1H), 7.91
(D; J = 5.7 Hz, 1H), 7.46-7.20
(M, 6H), 6.45 (d; J = 5.7 Hz, 1H),
4.09 (s, 2H), 3.52 (s, 3H)

Production Example 13 [3-benzylideneimino-
2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (a method for producing the present compound (49))] The present compound (1) (0.5 g, 1.11 mmol) and benzaldehyde (0 .24 g, 2.22 mmol) at 100 ° C. for 8 hours. Thereafter, the reaction mixture was cooled to room temperature. 5 m ethanol in the reaction mixture
The obtained crystals were collected by filtration, and 3-benzylideneimino-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (49)) was added.
0.39 g was obtained. m. p. 129.4 ° C

The structures of the compounds of the present invention are shown in Tables 1 and 2 together with the compound numbers. General formula 16

Embedded image Compound represented by

[0059]

[Table 1]

[0060]

[Table 2] [In Tables 1 and 2, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Ac represents an acetyl group, and Ph represents a phenyl group. ]

Next, formulation examples are shown. Parts represent parts by weight. Formulation Example 1 Compounds (1) and (2) of the present invention
(5), (7), (11), (15), (41) to (4)
9) 50 parts each, calcium lignin sulfonate 3
Parts, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain each wettable powder. Formulation Example 2 Compounds of the present invention (1), (2), (5), (7), (1)
1), (15), 20 parts of each of (41) to (49) and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and finely pulverized by a wet pulverization method. After that, in this, Xanthan gum 0.05
And 40 parts of an aqueous solution containing 0.1 part of aluminum magnesium silicate, and 10 parts of propylene glycol are further added and stirred and mixed to obtain each flowable preparation.

Formulation Example 3 Compounds (1), (2), (5), (7) and (1)
1), (15), 2 parts of each of (41) to (49), 88 parts of kaolin clay and 10 parts of talc are thoroughly pulverized and mixed to obtain each powder. Formulation Example 4 The present compound (1), (2), (5), (7), (1)
1), (15), 5 parts of each of (41) to (49), 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 7 parts of xylene
By mixing well 5 parts, each emulsion is obtained.

Formulation Example 5 Compounds of the present invention (1), (2), (5), (7), (1)
1), (15), 2 parts of each of (41) to (49), 1 part of synthetic hydrous silicon oxide, calcium lignin sulfonate 2
Parts, 30 parts of bentonite and 65 parts of kaolin clay are thoroughly crushed and mixed, water is added and well kneaded, and the mixture is granulated and dried to obtain each granule. Formulation Example 6 The present compounds (1), (2), (5), (7), and (1)
1), (15), 10 parts of each of (41) to (49), 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt, and 55 parts of water are mixed and finely pulverized by a wet pulverization method. By doing
Obtain each formulation.

Formulation Example 7 Compounds (1), (2), (5), (7) and (1)
1), (15), 0.1 part of each of (41) to (49) are dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this is mixed with 89.9 parts of deodorized kerosene to obtain 0.1% of each. Obtain an oil agent. Formulation Example 8 Compounds of the Present Invention (1), (2), (5), (7), (1)
1), (15), 0.1 part of each of (41) to (49),
10 parts of trichloroethane and 59.9 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, a valve part is attached, and then 30 parts of a propellant (liquefied petroleum gas) is filled under pressure through the valve part to make each oily. Get an aerosol.

Formulation Example 9 Compounds (1), (2), (5), (7), (1)
1), (15), 0.2 parts each of (41) to (49),
An aerosol container was charged with a mixture of 5 parts of xylene, 3.8 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (registered trademark of Atlas Chemical Co.)} and 50 parts of pure water, and a valve was attached. 40 parts of propellant (liquefied petroleum gas) is charged under pressure through the valve part to obtain each aqueous aerosol. Formulation Example 10 Compounds of the present invention (1), (2), (5), (7), (1)
1), (15), 100 mg of each of (41) to (49)
Was dissolved in an appropriate amount of acetone, and 4.0 cm × 4.0 cm,
Each heated smoke is obtained by impregnating a 1.2 cm thick porous ceramic plate.

Next, Test Examples show that the compound of the present invention is useful as an arthropod pest control agent. In addition, this invention compound is shown by the compound number of Table 1-2. The comparative compounds (A) and (B) represented by the following formulas (17) and (18) were used. These comparative compounds (A) and (B) are the compounds described in GB-1161492.

Embedded image Comparative compound (A)

Embedded image Comparative compound (B)

Test Example 1 Seven days after seeding, about 20 spider mites (Tetra) were placed on a plastic cup-planted thorny haricot (primary leaf stage).
nychus urticae) After releasing the adult female and leaving it to stand for 1 day, the compounds of the present invention (1), (2), (5),
(7), (11), (15), (41) to (43),
(45) to (49), aqueous diluents (50) of the preparations obtained according to Preparation Example 6 of each of comparative compounds (A) and (B)
(0 ppm), 20 ml, respectively. Fourteen days later, the number of live mites on the leaves of the beetle was examined, and the control rate was determined by the formula (I). As a result, each of the compounds of the present invention exhibited an effect of controlling the control rate of 90% or more. On the other hand, the control rates of the comparative compounds (A) and (B) were all 30
%. Formula (I) Control rate (%) = 100 × １００1− (Number of surviving mites in the treated section)
/ (Number of surviving mites in untreated area)｝

Test Example 2 A predetermined amount of the compound (1) of the present invention was dissolved in acetone, and 0.2 ml of the solution was dropped on a circular black paper having a diameter of 38 mm. After air-drying, it was spread on an aluminum plate having a bottom surface of 38 mm in diameter, and an adhesive was applied to the edge of black paper. Approximately 30 adult Dermatophagoides farinae adults were released on black paper and allowed to stand at 25 ° C. and 65% humidity. Twenty-four hours later, the number of surviving mites was investigated, and the control rate was determined by equation (II). Table 3 shows the results. Formula (II) Control rate (%) = 100 × １００1− (Number of living mites / (Number of test mites))

[0069]

[Table 3]

Test Example 3 Apple seedlings planted in plastic cups (about 6 months after sowing) were diluted with a water dilution (200 pp) of each of the compounds of the present invention (1) and (11) obtained according to Preparation Example 4.
m) 20 ml each were sprayed. After air drying, the apple seedlings (Adox)
ophies orana) 1st instar larvae were released. After 7 days, the number of surviving larvae on the leaves of the apple was examined, and the formula (II)
The control rate was determined according to I). As a result, each of the compounds of the present invention exhibited an effect of controlling the control rate of 90% or more. Formula (III) Pest control rate (%) = 100 × ｛1− (Number of surviving larvae in the treated section)
/ (Number of surviving larvae in untreated area)｝

[0071]

Industrial Applicability The compound of the present invention has an excellent arthropod pest control effect.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C055 AA01 BA02 BA52 BB04 BB07 CA02 CA51 CA52 CA53 CB01 CB02 CB07 CB08 DA42 DB04 DB07 4H011 AC01 AC02 AC04 BA01 BC03 BC06 BC07 BC09 BC18 DA02 DA13 DA15 DA16 DA21 DC01 DC05 DC06 DC08 DD03

Claims (5)

[Claims] 1. A compound represented by the general formula: [Wherein, R ¹ and R ² are the same or different and represent a halogen atom or a C1-C4 haloalkyl group, and n and m are the same or different and represent an integer of 1-3. However, when m represents an integer of 2 or more, R ¹ may be the same or different, and when n represents an integer of 2 or more, R ² may be the same or different. R ³ is a hydrogen atom, NR ⁴ R
⁵ ｛R ⁴ and R ⁵ are the same or different and are each a hydrogen atom, C1-
C4 alkyl group, C2-C5 alkoxyalkyl group, C
3-C4 alkanoyloxyalkyl group, C (= O) R
⁶ (R ⁶ represents a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C2-C4 alkoxyalkyl group, a C2-C4 alkoxycarbonyl group or a C3-C4 alkanoyloxyalkyl group)} or N = CR ⁷ R ⁸ ( R ⁷ represents a hydrogen atom or a C1-C4 alkyl group, and R ⁸ is a C1-C4
4 represents an alkoxy group or an optionally substituted phenyl group. ). A pyridine compound represented by the formula: 2. A haloalkyl group is a trifluoromethyl group,
The pyridine compound according to claim 1, which is a chlorodifluoromethyl group, a dichlorofluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, or a perfluorobutyl group. 3. An arthropod pest control agent comprising the pyridine compound according to claim 1 or 2 as an active ingredient. 4. A compound represented by the general formula: (Wherein, R ¹ , R ² , m and n represent the same meaning as described above). 5. A haloalkyl group is a trifluoromethyl group,
The pyridine compound according to claim 4, which is a chlorodifluoromethyl group, a dichlorofluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, or a perfluorobutyl group.