WO2001081313A1

WO2001081313A1 - Pyridine compounds, arthropod controllers containing the same as the active ingredient and intermediates for the preparation of the compounds

Info

Publication number: WO2001081313A1
Application number: PCT/JP2001/003015
Authority: WO
Inventors: Hiroki Tomioka
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2000-04-25
Filing date: 2001-04-06
Publication date: 2001-11-01
Also published as: AU2001244738A1

Abstract

Pyridine compounds of the following general formula; use of the same as arthropod controllers; and intermediates for the preparation thereof: wherein R?1 and R2¿ are each independently halogeno or C¿1-4? haloalkyl; n and m are each independently an integer of 1 to 3; and R?3¿ is hydrogen, NR4R5 (wherein R?4 and R5¿ are each independently hydrogen, C¿1-4? alkyl, or the like), or N=CR?7R8¿ (wherein R7 is hydrogen or C¿1-4? alkyl, and R?8¿ is C¿1-4? alkoxy or optionally substituted phenyl).

Description

Description Pyridine compound, arthropod control agent containing it as an active ingredient and intermediates thereof

The present invention relates to a pyridine compound, an arthropod-controlling composition containing the pyridine compound as an active ingredient, and a "Japanese" body.

Many insecticides have been developed and put into practical use, but their efficacy may not always be sufficient.

On the other hand, continuous use of the same type of drug in arthropod pests often leads to drug resistance problems.

Therefore, the development of new arthropod control agents having sufficient efficacy is desired. On the other hand, GB-1 169 492 describes that a certain 2,4-diphenoxypyridine derivative has pesticidal activity as a pesticide. Disclosure of the invention

The present invention provides a compound of the formula [I]

[Wherein, R ¹ and R ² are the same or different and represent a halogen atom or a C 1 -C 4 haloalkyl group, and n and m are the same or different and represent an integer of 1 to 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, formula NR ⁴ R ⁵ (where R ⁴ and R ⁵ are the same or different hydrogen atoms , (: 1-4 alkyl group, C 2 -C 5 alkoxyalkyl group, C 3 -C 4 alkyloxy group, C (= 〇) R ⁶ (R ⁶ is C 1 -C 4 alkyl group represents a C 1-C 4 haloalkyl group, C 2-C 4 alkoxyalkyl group, C 2-C 4 alkoxycarbonyl group or C 3-C 4 alkanoyloxy Noi Ruo alkoxyalkyl group.) or the formula N = CR ⁷ R ⁸ (R ⁷ represents a hydrogen atom or a C 1 -C 4 alkyl group, R ⁸ represents a C 1 -C 4 alkoxy group or a halogen atom, (: 1〇4 alkyl group, C 1 -C 4 alkoxy group , A C1-C4 haloalkyl group, a C1-C4 haloalkoxy group, a methylenedioxy group or a phenyl group which may be substituted with a C1-C4 alkylthio group.

A pyridine compound (hereinafter, referred to as the compound of the present invention), an arthropod controlling agent containing the compound of the present invention as an active ingredient, and a formula [II] which is an intermediate for producing the same.

(Wherein, RR ² , m and n represent the same meaning as described above.)

And a compound represented by the formula: In the compound of the present invention,

Examples of the halogen atom in R ′ and R ² include a fluorine atom and a chlorine atom, and examples of the C 1 -C 4 haloalkyl group include a trifluoromethyl group, a chlorodifluoromethyl group, and a dichlorofluoromethyl group. Group, perfluoroethyl group

Propyl group and butyl group.

Examples of the substituent at the 4-position of pyridine include 4-fluoro-3-trifluoromethylphenoxy, 4-chloro-3-trifluoromethylphenoxy, and 4-bromo-3-trifluoro. And trifluoromethylphenoxy group and 3-trifluoromethylphenoxy group. Examples of the substituent at the 2-position of pyridine include, for example, 4-fluoro-opening, 3-trifluoromethylphenoxy group and 4-chloro. Mouth—3-trifluoromethylphenoxy, 4-bromo-3-trifluoromethylphenoxy and 3- And a trifluoromethylphenoxy group.

Examples of the C 1 -C 4 alkyl group for R ⁴ and R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of 2-C 5 alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, isobutyloxymethyl and sec-butyloxymethyl, and C 3 -C 4 Examples of the alkanoyloxyalkyl group include an acetyloxymethyl group and a propionyloxymethyl group.

Examples of the C 1 -C 4 alkyl group for R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Examples of the C 4 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 C 4 alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group and an isopropoxymethyl group. Examples of the C 2 -C 4 alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. , A propoxycarbonyl group and an isopropoxycarbonyl group; The Noi Ruo alkoxyalkyl group, for example § cell Chiruokishimechiru group and a propionyloxy Ruo carboxymethyl group.

Note that the C 2-C 5 alkoxyalkyl group for R ⁴ and R ⁵ above, is meant a total carbon number of 2 to 5 Arco Kishiarukiru group, the C 3- C 4 Arukanoi Ruokishiarukiru group, Arukanoi It means that the total carbon number of the oxyalkyl group is 3 to 4. Also, the C 2-C 4 alkoxyalkyl group in R ^6, a total carbon number of the alkoxyalkyl group means that 2 to 4, and the C 2-C 4 Al Kokishikaruponiru group, the total of the alkoxycarbonyl group It means that the number of carbon atoms is 2 to 4, and the C3-C4 alkanoyloxyalkyl group means that the total number of carbon atoms of the alkanoyloxyalkyl group is 3 to 4.

The C 1-C 4 alkyl group in R ^7, for example a methyl group, is Echiru group and propyl group. Examples of the C 11 -C 4 alkoxy group for R ⁸ include a methoxy group, an ethoxy group and a propoxy group. Examples of the phenyl group which may be substituted include a phenyl group, a 2-chlorophenyl group, 4-methylphenyl, 4-ethoxyphenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 3,4-methylenedioxyphenyl and 4-methylthiophenyl Group.

Examples of the compound of the present invention include a compound having a 3-trifluoromethylphenoxy group in which a phenoxy ring may be further substituted at the 2-position of the pyridine ring, and a phenoxy ring at the 4-position of the pyridine ring. A compound having an optionally substituted 3-trifluoromethylphenoxy group, a compound having an optionally substituted 3-trifluoromethylphenoxy group at the 2- and 4-positions of a pyridine ring, pyridine A compound having a 4-halo-3-trifluoromethylphenoxy group at the 2-position of the ring, a compound having a 4-halo-3-trifluoromethylphenoxy group at the 4-position of the pyridine ring, and a compound having a pyridine ring at the 4-position Compounds having a 4-halo-3-trifluoromethylphenoxy group at the 2- and 4-positions are exemplified.

The compound of the present invention can be produced, for example, according to the following (Production method 1) to (Production method 6).

(Production method 1)

In the compound of the present invention represented by the formula [I], R ³ is NR ⁴ — ′ R ⁵ — ¹ (R ⁴ and R ⁵ ^—1 are a C 1 -C 4 alkyl group and a C 2 -C 5 alkoxyalkyl group, respectively. , C3- C 4 alkanoyloxy Noi Ruo alkoxyalkyl group or a ^{C (= 0) R 6 (} R 6 is C 1-C4 alkyl group, C 1-C 4 haloalkyl group, C 2-C 4 alkoxyalkyl group, C2-C4 Represents an alkoxycarbonyl group or a C 3 -C 4 alkanoyloxyalkyl group.

Among the compounds of the present invention represented by the formula [I], the compound wherein R ³ is NR ⁴ ^—1 R ⁵ ^—1 is a compound of the formula [III]

^{(Wherein, R ', R 2, m} , n are as defined above, R ^{4 1} is C 1-C 4 alkyl le group, C 2-C 5 alkoxyalkyl group, C 3- C 4 Arukanoi Roxyalkyl group or C (= 0) R ⁶ (R ⁶ is a C 1 C 4 alkyl group, CI—C 4 haloalkyl group, C 2—C 4 alkoxyalkyl group, C 2—C 4 alkoxycarbonyl group Represents a C 3 -C 4 alkanoyloxyalkyl group.

And an amine compound of the formula [IV]

R ⁵ - ¹ Z

(Wherein, R ^{5 1} is C 1-C 4 alkyl, C 2-C 5 alkoxyalkyl group, C 3-C 4 alkanoyloxy Noi Ruo alkoxyalkyl group or a ^{C (= 0) R 6 (} R 6 is C 1 —C 4 alkyl group, C 1 -C 4 haloalkyl group, C 2 -C 4 alkoxyalkyl group, C 2 -C 4 alkoxycarbonyl group or C 3 -C 4 alkanoyloxyalkyl group. Z is, R ^{5 1} represents a halo gen atom in the case of C 1-C 4 alkyl group, C 2-C 5 alkoxy Shiarukiru group or a C 3- C 4 alkanoyloxy Noi Ruo alkoxyalkyl group, R ^{5 1} is When C (= 0) R ⁶ represents a halogen atom or an OC (= 0) R ⁶ group.)

The compound can be produced by reacting a compound represented by the following formula:

The reaction is usually performed in an inert 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.

Specific examples of the solvent inert to the reaction used in the reaction include 1,4 dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl ether, ethers such as tert-butyl methyl ether, hexane, Aliphatic hydrocarbons such as heptane, lignin, petroleum ether, aromatic hydrocarbons such as toluene and xylene, N, N dimethylform Acid amides such as muamide and the like, and mixtures thereof.

The amount of the compound represented by the formula [IV] used in the reaction is about 1 mol per 1 mol of the compound represented by the formula [III], but may be changed according to the reaction conditions. be able to.

The amount of the base used in the reaction may be about 1 mol per 1 mol of the compound represented by the formula [III], but may be changed depending on the reaction conditions. The reaction temperature is usually in the range of-30 to 120.

The reaction time is usually between 0.1 and 100 hours.

After the reaction, the compound of the present invention can be isolated, for example, by performing the following post-treatment.

1. Pour the reaction mixture into water, extract with an organic solvent, and concentrate. If necessary, perform purification procedures such as chromatography and recrystallization.

2. Concentrate the reaction solution as is, and if necessary, further purify by chromatography, recrystallization, etc.

(Production method 2)

Method for producing compound represented by formula [III]

The compound represented by the formula [III] is represented by the formula [V]

(Wherein, RR ² , m, and n represent the same meaning as described above.)

And a compound represented by the formula [VI]

R ^4- 'Z

(Wherein, R ⁴ — ¹ is a C 1 -C 4 alkyl group, C 2 —C 5 alkoxyalkyl group, C 3 — C 4 alkanoyloxyalkyl group or C (= 0) R ⁶ (R ⁶ is C 1 Represents a C 4 alkyl group, a C 1 -C 4 haloalkyl group, a C 2 -C 4 alkoxyalkyl group, a C 2 -C 4 alkoxycarbonyl group or a C 3 -C 4 alkanoyloxyalkyl group. ⁴ - ¹ C 1-C 4 alkyl group, C 2-C 5 Arukokishia A halogen atom when R ⁴ — ¹ is a C (= 0) R ⁶ group, a halogen atom or OC (= 0) when R ⁴ — ¹ is a C (= 0) R ⁶ group. ) R ⁶ represents a group. )

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.

Specific examples of the inert solvent used in the reaction include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl ether, tert-butyl methyl ether, and the like. Examples include aliphatic hydrocarbons such as xane, heptane, lignin, and petroleum ether, aromatic hydrocarbons such as toluene and xylene, acid amides such as N, N-dimethylformamide, and mixtures thereof. .

The amount of the compound represented by the formula [VI] used in the reaction is sufficient to be about 1 mol per 1 mol of the compound represented by the formula [V], but may be changed according to the reaction conditions. it can.

The amount of the base used in the reaction is about 1 mol per 1 mol of the compound represented by the formula [V], but it can be changed according to the reaction conditions.

The reaction temperature is usually in the range of 130 to 120.

The reaction time is usually between 0.1 and 100 hours.

1. A method in which the reaction solution is poured into water, extracted with an organic solvent, concentrated, and then, if necessary, further purified by chromatography, recrystallization, or the like.

2. A method in which the reaction solution is concentrated as it is and, if necessary, further purified, such as chromatography and recrystallization.

When the compound represented by the formula [III] is used as the starting compound of the above-mentioned (Production method 1), the product is not isolated and the reaction of the (Production method 2) is carried out immediately after the reaction of (Production method 2). The reaction of production method 1) can also be carried out.

(Production method 3)

Method for producing compound of formula [V] among compounds of the present invention

The compound represented by the formula [V] is represented by the formula [II]

(Wherein, RR ² , m, and n represent the same meaning as described above.)

Can be produced by subjecting a ditropyridine compound represented by the following formula to a reduction reaction. The reduction reaction can be carried out, for example, by the following (Production method 3-1) and (Production method 3-2).

(Production method 3-1)

A method of subjecting a compound represented by the formula [II] to a reduction reaction using a metal or a metal halide in the presence of acidic water.

The reduction reaction is performed without solvent or in an inert solvent.

Examples of the acidic water used for the reduction reaction include hydrochloric acid, aqueous sulfuric acid and aqueous acetic acid, and examples of the metal or metal halide include zinc, tin, iron and stannous chloride.

Examples of the solvent that can be used in the reduction reaction include alcohols such as methanol, ethanol, and propanol, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, getyl ether, and tert-butyl methyl ether. And the like, esters such as ethyl acetate and methyl propionate, and mixtures thereof. The amount of acidic water used for the reduction reaction can be changed according to the reaction conditions, but is usually an excess amount, and the amount of a simple metal or a metal halide is usually represented by the formula [II]. The ratio is 3 to 10 mol per 1 mol of the compound.

The temperature of the reduction reaction is usually in the range of 0 to 15 Ot :.

The reaction time is usually from 0.5 to 100 hours. After the reaction, the compound of the present invention can be isolated by performing the following post-treatment operations.

1. Pour the reaction solution into water, neutralize with a base (eg, aqueous ammonia), filter, extract the filtrate with an organic solvent, and concentrate. If necessary, perform purification operations such as chromatography and recrystallization.

2. Pour the reaction mixture into water, extract with an organic solvent, and concentrate. If necessary, perform purification procedures such as chromatography and recrystallization.

(Production method 3-2)

A method of subjecting a compound represented by the formula [II] to a reduction reaction with hydrogen in the presence of a transition metal catalyst

The reduction reaction is usually performed in an inert solvent.

The transition metal catalyst used in the reduction reaction, for example PdZC, PdZS r C 〇 ₃ include P t 0 ₂ and Raney nickel.

Specific examples of solvents inert to the reaction used in the reaction include alcohols such as methanol, ethanol and propanol, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and getyl. Ethers such as ether and tert-butyl methyl ether; 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 per 1 mol of the compound represented by the formula [Π], and the amount of hydrogen is usually represented by the formula [II]. A ratio of about 3 moles per mole of the indicated compound is sufficient.

The reduction reaction temperature is usually in the range of 0 to 15.

The reaction time is usually 0.5 to 100 hours.

After the reduction reaction, the compound of the present invention can be isolated by performing the following post-treatment operations.

1. Filter the reaction solution and concentrate the filtrate. Further, if necessary, further purification operations such as chromatography and recrystallization are performed.

2. Pour the reaction mixture into water, extract with an organic solvent, and concentrate. If necessary, click Perform refining operations such as oral chromatography and recrystallization.

(Production method 4)

Method for producing a compound of the present invention represented by the formula [I], wherein R ³ is a hydrogen atom

Among the compounds of the present invention represented by the formula [I], compounds in which R ³ is a hydrogen atom can be obtained by converting the compound represented by the formula [V] to ethers (eg, tetrahydrofuran, getyl ether, 1,4-dioxane and ethylene glycol dimethyl ether) Formula [VII] in the presence of

R ⁹ ON0 ₂

(In the formula, R ⁹ represents a C 1 -C 5 alkyl group.)

By reacting nitrites represented by The reaction is performed without solvent or in an inert solvent.

Examples of nitrites that can be used in the reaction include, for example, isoamyl nitrite, isobutyl nitrite, and t-butyl nitrite.

The reaction can be carried out using ethers in a solvent amount, and a solvent inert to the reaction can be used together.

The amount of the nitrite used in the reaction is about 1 mol per 1 mol of the compound represented by the formula [V], but can be changed according to the reaction conditions. The reaction temperature is usually in the range of 0 to 150 ° C.

The reaction time is usually 0.5 to 100 hours.

After the reaction, the compound of the present invention can be isolated by performing the following post-treatment operations.

1. Concentrate the reaction solution as it is. If necessary, purification operations such as chromatography and recrystallization are further performed.

2. Pour the reaction mixture into water, extract with organic solvent, and concentrate. If necessary, perform purification operations such as chromatography and recrystallization.

(Production method 5)

In the compound of the present invention represented by the formula [I], R ³ represents a formula N = CR ⁷ R ⁸ (R ⁷ represents a hydrogen atom or a C 1 -C 4 alkyl group, and a rule ⁸ represents a 〇 1 -C 4 alkoxy group. Represent ) Method for producing the compound shown

In the compound of the present invention represented by the formula [I], R ³ represents a formula N = CR ⁷ R ⁸ (R ⁷ represents a hydrogen atom or a C 1 -C 4 alkyl group, and R ⁸ represents a C 1 -C 4 alkoxy group) Is a compound represented by the formula [V] and a compound represented by the formula [VIII]

CR ⁷ (OR ¹⁰ ) 3

(In the formula, R ⁷ represents a hydrogen atom or a C 1 -C 4 alkyl group, and R ^1G represents a CI-C 4 alkyl group.)

By reacting with an orthoester represented by the formula (1) in the presence or absence of an acid catalyst.

The reaction is performed without solvent or in an inert solvent.

Examples of the orthoesters that can be used in the reaction include, for example, methyl orthoformate, ethyl ethyl formate, methyl orthoacetate, ethyl ethyl orthoformate, oral pill, ethyl ethyl orthopropionate, methyl ethyl orthobutyrate, and methyl orthovalerate. Le.

Examples of the acid catalyst used in the reaction include inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as acetic acid and p-toluenesulfonic acid.

In the reaction, a large excess of orthoesters can be used as a solvent, but other solvents inert to the reaction can also be used. Specific examples of the inert solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl ether, tert-butyl methyl ether, hexane, heptane, lignin, petroleum oil. Aliphatic hydrocarbons such as ethers, aromatic hydrocarbons such as toluene and xylene, N

And acid amides such as N, N-dimethylformamide and mixtures thereof. The amount of the orthoester used in the reaction is from 1 mol to an excess amount per 1 mol of the compound represented by the formula [V].

Reaction temperatures are usually in the range of 0 to 150.

The reaction time is usually 0.5 to 100 hours.

After the reaction, the compound of the present invention can be isolated by performing the following post-treatment operations. 1. Concentrate the reaction solution as it is. If necessary, purification operations such as chromatography and recrystallization are further performed.

(Production method 6)

In the compound of the present invention represented by the formula [I], R ³ is a group represented by the formula N = CR ⁷ R ⁸ (R ⁷ represents a hydrogen atom or a C 1 -C 4 alkyl group, and R ⁸ is a phenyl which may be substituted. A method for producing the compound represented by

In the compound of the present invention represented by the formula [I], R ³ is a formula 1 ^ = 1 ^ ⁷ ¹⁸ (R ⁷ represents a hydrogen atom or a C 1 -C 4 alkyl group, and R ⁸ may be substituted A compound represented by the formula [V] and a compound represented by the formula [IX]

R ⁷ (C = 0) R ¹¹

(In the formula, R ⁷ represents a hydrogen atom or a C 1 -C 4 alkyl group, and R ¹¹ represents a phenyl group which may be substituted.)

Can be produced by reacting with a carbonyl compound represented by

The reaction is performed without a solvent.

Examples of carbonyl compounds that can be used in the reaction include benzaldehyde, 2-chlorobenzaldehyde, 4-ethoxybenzaldehyde, p-tolaldehyde, 4-trifluoromethylbenzaldehyde, and 3,4-methylenedioxy. Benzaldehyde, 4-trifluoromethoxybenzaldehyde, 4-methylthiobenzaldehyde and acetofphenone.

In the reaction, a large excess of carbonyl compounds can be used as a solvent. The amount of the carbonyl compound used in the reaction is from 1 mol to an excess amount per 1 mol of the compound represented by the formula [V].

The reaction temperature is usually in the range of 0 to 150 ° C.

The reaction time is usually 0.5 to 100 hours.

2. Pour the reaction mixture into water, extract with organic solvent, and concentrate. If necessary, perform further purification operations such as chromatography and recrystallization.

3. Leave the reaction solution at room temperature, and filter out the precipitated crystals. Next, a method for producing the compound represented by the formula [II], which is an intermediate of the compound of the present invention, will be described.

The compound represented by the formula [Π] is prepared by combining 2,4-dichloro-3-nitropyridine with a compound of the formula [IX]

(Wherein, R ² and n represent the same meaning as described above.)

Is reacted with a phenolic compound represented by the formula in the presence of a base to give a compound of the formula [X]

(Wherein, R ² and n represent the same meaning as described above.)

(The first step), and then the obtained compound represented by the formula [X] and the formula [XI]

(Wherein, R ¹ and m represent the same meaning as described above.)

(The second step) by reacting the phenolic compound represented by the formula with a base in the presence of a base.

First, the first step will be described. The reaction is usually performed in an inert solvent in the presence of a base.

Solvents inert to the reaction used in the reaction include, for example, ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl ether, tert-butyl methyl ether, and hexane. And aliphatic hydrocarbons such as heptane, lignin, and petroleum ether; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide; and mixtures thereof.

The amount of the phenolic compound of the formula [IX] used in the reaction is about 1 mol per 1 mol of 2,4-dichloro-3-nitropyridine, but it is varied depending on the reaction conditions. be able to.

The reaction temperature range is usually in the range of 0 to 150.

The reaction time is usually between 0.5 and 100 hours.

The amount of the base used in the reaction is sufficient in a ratio of about 1 mol per 1 mol of the phenol compound represented by the formula [VIII], but can be changed according to the reaction conditions.

After the reaction, the reaction mixture is poured into water, subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, and, if necessary, further purification operations such as chromatography and recrystallization, whereby the desired product is obtained. The compound represented by the formula [X] can be obtained. In addition, the reaction solution containing the target compound represented by the formula [X] can be used in the second step without performing a post-treatment operation.

Next, the second step will be described.

Solvents inert to the reaction used in the reaction include, for example, 1,4-dioxane Ethers such as styrene, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl ether, tert-butyl methyl ether; hexane, heptane, rig-mouth, aliphatic hydrocarbons such as petroleum ether, toluene, Examples include aromatic hydrocarbons such as xylene, N, N-dimethylformamide, and the like, and mixtures thereof.

The amount of the phenolic compound represented by the formula [XI] used in the reaction is about 1 mol per 1 mol of the compound represented by the formula [X], but it should be changed according to the reaction conditions. Can be.

The amount of the base used in the reaction is sufficient at about 1 mol per 1 mol of the phenol compound represented by the formula [XI], but can be changed according to the reaction conditions.

The reaction temperature is usually in the range of 0 to 15 Ot :.

The reaction time is usually between 0.5 and 100 hours.

After the reaction, the reaction solution is poured into water, subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, and, if necessary, purification and purification procedures such as chromatography and recrystallization. The compound represented by the formula [II] can be isolated.

2,4-Dichloro-3-nitropyridine serving as a raw material can be produced, for example, by the method described in International Patent Publication WO99 / 40991.

Although the compound of the present invention can be used as it is for controlling arthropods, it is usually used in the form of a formulation.

Examples of the preparation include solid preparations such as granules, powders and wettable powders, and liquid preparations such as oils, emulsions, flowables and microcapsules. The amount of the compound of the present invention, which is an active ingredient, contained in the arthropod control agent of the present invention is usually from 0.01% to 95% by weight, depending on the preparation.

The arthropod control agent of the present invention can be obtained by mixing the compound of the present invention and a carrier, blending a surfactant, a fixing agent, a thickener, a stabilizer, and the like, if necessary, and performing pulverization, processing, and the like. be able to.

Carriers used in such formulation include, for example, clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.) , Talc, ceramics, solid carriers such as sericite, quartz, activated carbon, carbonated calcium carbonate, hydrated silica, montmorillonite, etc., water, alcohols (methanol, ethanol, ethylene glycol, propylene glycol, etc.), Ketones (acetone, methylethylketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, phenylxylylethane, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene) , Gas oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N , N-dimethyla Toamides), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), liquid carriers such as vegetable oils such as dimethyl sulfoxide, soybean oil, cottonseed oil, etc., and CFCs, butane gas, LPG (liquefied petroleum gas), Gaseous carriers such as dimethyl ether and carbon dioxide can be used.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, polyoxyethylenates of alkyl aryl ethers, polyethylene glycol ethers, and the like. Examples include polyhydric alcohol esters, sugar esters, and sugar alcohol derivatives.

Examples of the fixing agent include casein, gelatin, polysaccharides (starch, arabia gum, xanthan gum, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, and synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, Examples of the thickener include polysaccharides (such as xanthan gum) and inorganic minerals (such as aluminum magnesium silicate). Stabilizers include, for example, PAP ( Isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), Vegetable oils, mineral oils, fatty acids, and fatty acid esters That.

Examples of the method of using the preparation which is the arthropod control agent of the present invention include the following methods. It can be appropriately selected according to the dosage form of the preparation, the place of use, and the like.

1. The method of treating the preparation as it is in the habitat of the pest.

2. A method in which the drug product is diluted with a solvent such as water and then treated at the pest's habitat.

3. A method in which the preparation is heated in the habitat of the pest to volatilize the active ingredient.

In addition, the arthropod control agent of the present invention can be used in combination with other insecticides, nematicides, acaricides, or the like without mixing or premixing.

Examples of the active ingredients of such insecticides, acaricides and nematicides that can be used in combination or in combination are, for example, funitrothion, fenthion, diazinon, chlorpyrifos, acephate, methidathion, disulfoton, DDVP, sulprophos, profenophos, cyanophos, Organophosphorus compounds such as dioxabenzophos, dimethoate, fentoate, malathion, trichlorfon, azinphosmethyl, monocrotophos, ethione, phosthiazate, BPMC, benfracarp, proboxixur, carbosulfan, carbofuran, caplevalyl, mesomil, ethimil Carbamate compounds such as offencarp, aldicarp, oxamyl, phenothocarp, thiodicarp and aranicarp;

Etofenprox, halfphenprox, fenvalerate, esfenvalerate, fenpropatrin, cypermethrin, alpha cypermethrin, ze overnight cypermethrin, permethrin, cyhalothrin, lambda cyhalothrin, deltamethrin, cycloprothrin, ufurbari Pyrethroid compounds such as catenate, flucitrinate, bifenthrin, acrinatrine, sifurretrin, 3-cyfurretrin, tralomethrin, and silafluofen;

Neonicotinoid compounds such as acetamiprid, thiamethoxam, and ditenviram; thiadiazine derivatives such as buprofezin; nepalitoxin derivatives such as cartap, thiocyclam and vensultap; chlorinated hydrocarbon compounds such as endosulfan and αBHC; chlorflua Zuron, Teflupenzuron, Flufenox mouth, Hexaflumuron, Rufenuron, etc., Benzoylphenylperylene-based compounds, Amitraz, Chlodimethyleform, etc., Formamidine derivatives, Phenylpyrazol-based compounds, Tebufenozide, Methoxyphenozide, Halofenozide Phenylhydrazine derivatives such as enozide, chlorphenavir, bromoprovire , Propargite, fenbutatin oxide, hexthiazox, clofuentezine, ethoxazole, acequinosyl, bifenazate, pyridaben, fenpyroximate, diafenthiuron, tebufenpyrad, pyrimidifene, phenazaquin, polynactin, quinactin, nactin Examples include milbemectin, evamectin, emamectin benzoate, azadirachtin, pymetrozine, indoxacarp, and spinosyn derivatives. Examples of the harmful insects and harmful mites that can be controlled by the arthropod control agent of the present invention include the following.

Hemiptera: insects (Laodelphax striatellus), flying squirrels (Nilaparvata lugens), staghorn planthoppers (Sogatella furcifera), etc.,ヮ Evening aphids (Aphis gossypi i), peach aphids (Myzus persicae), Mycamide aphids (Aphis citricola), Nisedai aphids (Lipaphis pser udobrassicae), Nashimidorio aphids (Nippolachnus aurica) i), Citrus aphid (Toxoptera ci id ius), etc.}, Stink bugs (Nezara antennata), Hosoharika beetles (Cletus punct iger), Hosohelika beetles (Riptortus clavetus), Chiba beetle stalls Etc.) Whiteflies {Treureurodes vaporar iorum), evening whiteflies (Bemisia tabaci), silverleaf whiteflies (Bemisia argent i fol iί), etc.} (Comstockaspis perniclosa), Citrus scampi (Unaspis ci tri), Pseuclaulacaspis pentagona, Olive mosquitoes (Saissetia oleae), Mandarin oysters (Lepidosaphes becki i), Rubiiroum (Ceroplastes rubens), Icerya pur chasi, etc.}, Dermatophagoides, lice.

Lepidopteran pests: Japanese bats (Chilo suppressalis, Cnaphalocrocis medinal is), Ostr inia nub ilalis), Shibataga (Parapediasia teterrella), ヮノメイ (Notarcha derogata), シメ P (Plodia interpunctel la), etc., ガ, ガ (Spodoptera 1 itura), ヮ se se （ Pegasus (Mamestra brassicae), Tamanaya force (Agrotis ipsilon), Trichoprusia, Heliotis, Helicoverpa, etc.}, White butterfly {Pierris rapae), etc.}, Anopheles {Adoxofujes, Grapholita molesta), codling moth (Cydia pomonella), etc., squirrel moths (Carposina niponensis), etc., haemoglygaes (genus Rionetia, etc.), dog moths (genus Limantria, uprocutis, etc.), cormorants (konaga) (Plutella xylostella), etc., and Kibaga (Pect inophora gossypiella, etc.), Trigger such {Hyphantria Arctiidae (Hyphantria cunea), etc.), Hirozukoga acids {I moth (Tinea translucens), Koiga (Tineola bisselliella), etc.} and the like.

Diptera: Pests {Culex pipiens pallens, Culex tr i taeniorhynchus, etc.}, Aethes ((Aedes aegypt i), (Aedes albopictus), etc.), Anopheres { (Anopheles sinensis), etc.}, Musca domestica, Musca domestica (Musca domestica, Musca domestica), etc. antiqua), etc.), fruit flies, Drosophila, melanogaster, butterflies, buchus, flies, sand flies, and mosquitoes.

Coleoptera pests: Scarabaeids {Anomala cuprea, Anomala rufocuprea, etc.}, Scorpion beetles (Sitophilu s zeamais), Izumi mizozo, "Lissor phi lusor zo, Lissor hopulas zo, Lissor hoplus zo res," Hypera pastica), Azukizomushi (Cal losobruchuys ch ienensis), etc.}, Tenebrion beetles {Tenebrio molitor, Tribolium castaneum, etc.) Devil (Phyl loireta striolat a), Colorado potato beetle (Lept inotarsa deceml ineata), Western corn relay Mumworm (Diabrotica virgi fera virgi fera), Southern corn relate (Diabrot ica undeciinpunctata howardi), etc.}, Synopsis, Echiracuna {Epilachna vigint ioctopunctata, etc.} , Long-tailed beetles, Longicorn beetles, Avovariga evening beetles (Paederus fuscipes).

Cockroach pests: German cockroaches (Blattella germanica), black cockroaches (Periplaneta ful iginosa), red cockroaches (Per iplaneta amer icana), brown cockroaches (Periplaneta brunnea), and black cockroaches (Blatta orie ntalis).

Thrips palmiform pests: Thrips palmi (Thrips palmi), Nekozami (Thrips tabaci), Thrips thrips (Thrips a ai iensis), Chestnut yellow thrips (Scirtothrips dorsalis), Hirazana inu Yellow thrips (Frankl iniel la occidental is), power thrips (Ponticulothrips diospyrosi), etc.

Hymenopteran pests: squirrels, hornets, squirrels, and wasps {such as Athalia japonic a).

Orthoptera pests: Kera, basidae, etc.

Laminariae pests: cat flea (Ctenocephalides felis), wild flea (Ctenocephal id es canis), wild flea (Pulex i rri tans) and the like.

Louse pests: White lice (Pediculus humanus corporis), lice (Phthirus pubis) and the like.

Termite pests: termites (Reticulitermes speratus), house termites (Coptotermes formosanus) and the like.

Acarid pests: two spiders {Tetranychus urticae, Tetranychus kanzawai, mandarin mites (Panonychus ci tri), Rincono, mites (Panonychus ulmi), etc.}, genus Brevipalpus Two types of squirrels (Polyphagotarsonemus latus, etc.), ticks (Aculopus pelekassi), Tyanosahii (Calacarus carinatu s), etc., ticks (Haemaphyxal isoric)ゥ Ticks (Boophilus microplus), etc.}, mites (Tyroph agus putrescentiae, etc.), Dermatophagoides (Dermatophago ides farinae), Dermatophagoides ticks (Dermatophago ides pternyssss) (Cheyletus for Us), cucumber mites (Cheyletus malaccensis), southern mites (Cheylet us moorei), etc., and mites.

It is also effective against pests that have developed resistance to existing acaricides. Example

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 described. The numbers of the compounds of the present invention are the compound numbers described in Tables 1 and 2 below.

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-13-ditropyridine (0.39 g, 2 mmol) and 4-fluoro-3--3-trifluoromethylphenol (0.72 g, 4 mmol) were added to N, N-dimethylformamide (20 ml). After dissolution, 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 layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give 2,4-di (4-fluoro-3-trifluoromethylphenoxy) -1,3-nitropyridine. Obtained.

1 H-NMR (250 MHz; CDC 1 TMS): δ (p pm) 8.06 (d; J = 5.8 Hz, 1H), 7.53-7.22 (m, 6H), 6.50 (d; J = 5.8 Hz) , 1 H)

The obtained 2,4-di (4-fluoro-3-trifluoromethylphenoxy) -13-nitropyridine was directly used in the next step.

(2nd step) The 2,4-di (4_fluoro-3-trifluoromethylphenoxy) —3-nitropyridine obtained in the first step is dissolved in dimethyl ether (2 ml), and stannous chloride is added to this solution. A solution of 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, and neutralized with aqueous ammonia. Ethyl acetate was added to this, and the insolubles were removed by filtration through celite, followed by liquid separation. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was subjected to silica gel chromatography to obtain 0.34 g of 3-amino-1,2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (the present compound (1)). .

m.p.83.9t

¹ H-NMR (300 MHz; CDC 1 TMS) δ (p pm): 7.46 (d; J = 5.7 Hz, 1H), 7.45-7.20 (m, 6H), 6.42 (d; J = 5.7 Hz, 1 H), 4.06 (b r.s, 2H)

Production Example 2 [2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (Production method of compound (2) of the present invention]]

Dissolve 3-amino-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (0.23 g, 0.51 mmol) in tetrahydrofuran (5 ml) and add nitrous acid at 50-60 ° C. A solution of butyl (58 mg, 0.56 mmol) in tetrahydrofuran (0.5 ml) was added dropwise over 20 minutes. After the addition was completed, the mixture was heated to reflux for 3 hours. Thereafter, the reaction mixture was cooled, concentrated under reduced pressure, and the residue obtained 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.

m.p.66.4

¹ H-NMR (300 MHz; CDC 1 TMS) δ (p pm): 8.04 (d; J = 5.7 Hz, 1H), 7.45-7.19 (m, 6 H), 6.63 (dd; J = 5.7 , 1.8Hz, 1H), 6.41 (d; J = 1.8Hz, 1H)

Production Example 3 [3-acetoamide-2,4-di (4-fluoro-3-trifluoroacetone) Tylphenoxy) pyridine (Compound (5) of the present invention) and 3-diacetylamino-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (Method of producing compound (11) of the present invention)

3-Amino-1,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (0.25 g, 0.55 mmol) is dissolved in toluene (5 ml) and dried under ice-cooling. Acetic acid (0.15 g, 1.47 mmol) and pyridine (0.16 g, 2.0 mmol) were added dropwise. Thereafter, the mixture was stirred at room temperature for 12 hours and further heated and refluxed for 12 hours. After the reaction solution was cooled to room temperature, it 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. The resulting residue was subjected to silica gel column chromatography to give 93 mg of 3-diacetylamino-2,4-di (4-fluoro-3_trifluoromethylphenoxy) pyridine (compound of the present invention (11)) and 3-acetoacetate Mido-1,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridin (the present compound (5)) 12 Omg was obtained.

3-Diacetylamino-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine

m.p. 1 13.O:

Ή-NMR (250 MHz; CDC 1 3 / TMS) δ (p pm):. 8. 04 (d; J = 5. 8Hz, 1H), 7. 41 -7 20 (m, 6H), 6. 48 (d; J = 5.8Hz, 1H), 2.45 (s, 6H)

3-acetamide 1,2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine

m.p. 153.8

^{1 H-NMR (300MHz; CDC} 1 3 ZTMS) δ (m): 7. 88 (d; J = 5. 7Hz, 1H), 7. 54- 7. 02 (m, 6H), 6. 43 (d J = 5.7 Hz, 1 H), 2.84 (br. S, 1 H), 2.22 (s, 3H) Production Example 4 [3-Trifluoroacetamido-2,4-di (4- Method for producing fluoro-3-trifluoromethylphenoxy) pyridine (compound (7) of the present invention) 3-amino-1,2,4-di (4-fluoro-3-trifluoromethylphenoxy) Pyridine (0.18 g, 0.4 mmol) 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 under ice cooling. Mmol) was added dropwise. Thereafter, the mixture was stirred at room temperature for 12 hours. The reaction solution was directly concentrated under reduced pressure, and the residue obtained was subjected to silica gel column chromatography to give 3-trifluoroacetamide-1,2,4-diamine.

(4-monofluoro-3-trifluoromethylphenoxy) pyridine (compound of the present invention

(7)) 0.18 g was obtained.

m. p. 126. It:

¹ H-NMR (300 MHz; CDC 1 TMS) δ (ppm): 7.97 (d; J = 5.7 Hz, 1H), 7.92 (br.s; lH), 7.48-7 .22 (m, 6H), 6.45 (d; J = 5.7Hz, 1H)

Production Example 5 [Production method of 3- (N-acetyl-N-butyrylamino) 1-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (compound (15) of the present invention]

The compound (5) (0.308) and pyridine (0.059 ml) were dissolved in toluene (10 ml), and putyryl chloride (0.07 Oml) was added thereto with stirring at room temperature. Then, after stirring at room temperature for 3 hours, the mixture was heated and refluxed for 12 hours. The temperature of the reaction solution was returned to room temperature, acidified with 10% aqueous hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed sequentially with 10% aqueous hydrochloric acid, saturated saline and saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product is purified by silica gel column chromatography, and 3- (N-acetyl-N-butylylamino) -2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine

(Compound of the present invention (15)) 0.24 g was obtained.

70% yield

n _D ²⁴ - ⁵ 1. 495 1

Production Example 6 [Method for producing 3- (N-ethoxymethyleneamino) -12,4-di (4-fluoro-13-trifluoromethylphenoxy) pyridine (compound (41) of the present invention)

Dissolve 0.20 g of compound (1) in 5 ml of triethyl orthoformate, and add 70-80 For 6 hours. Then, excess triethyl orthoformate was distilled off under reduced pressure to obtain crude crystals. The crude crystals were recrystallized from a mixture of hexane: ethyl acetate = 1: 0: 1 to give 3- (N-ethoxymethyleneamino) -1,2,4-di (4-fluoro □ -3) Trifluoromethylphenoxy) pyridine (the present compound (41)) (0.10 g) was obtained.

Yield 45%

m.p. 135.4 *

Production Example 7 [Production method of 2,4-di (4-monofluoro-3-trifluoromethylphenoxy) -3- (N-methoxymethyleneamino) pyridine (Compound (42) of the present invention]

0.20 g of the compound (1) was dissolved in 5 ml of trimethyl orthoformate, and the mixture was stirred with heating at 70 to 80 "C for 6 hours. Thereafter, excess trimethyl orthoformate was distilled off under reduced pressure to obtain crude crystals. The crude crystals are washed with hexane, and 2,4-di (4-monofluoro-3-trifluoromethylphenoxy) -3- (N-methoxymethyleneamino) pyridine (compound (42) of the present invention) 0.16 g was obtained.

74% yield

mp 1 29.2 °

Production Example 8 [3- (N-ethylamino) -1,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (Compound (43) of the present invention) and 3- (N, N-ethylamino) ) Method for producing 1,2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (compound (44) of the present invention)

0.30 g of the compound (1) was dissolved in 3 ml of N, N-dimethylformamide, 0.092 g of potassium carbonate was added, and 0.053 ml of ethane was added dropwise with stirring at room temperature. Thereafter, the mixture was stirred at room temperature for 9 hours, and then stirred at 60 for 4 hours. After adding 0.1 lm 1 of potassium carbonate and stirring at 60 for 1 hour, 0.1 g of potassium carbonate was added and the mixture was stirred at 60 for 1 hour. Further, 0.1 ml of eodoethane and 0.1 g of potassium carbonate were added, and the mixture was stirred at 60 for 1 hour. The temperature of 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 brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a crude product. This crude product is converted to silica Purification by gel column chromatography gave 3- (N-ethylamino) 1-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine (compound of the present invention (43) 0.020 g (yield rate 6%, ^ -NMR (CDC 1 3, TMS, <5 (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—Jetylamino) —2, 4—di (4 - Furuoro 3 triflate Ruo Russia methyl phenoxyethanol) pyridine (present compound (44)) 0. 17 g ( 50% _{^{^{yield, n D 24 - 5 1. 5079}}} ) was obtained.

Production Example 9 [3-Amino-1,2,4-di (4-chloro-3-3-trifluoromethylphenoxy) pyridine] (Method for producing compound (45) of the present invention)]

The same procedure was followed except that 4-monocloth-3-trifluoromethylphenol was used in place of 4-fluoro-3-trifluoromethylphenol in Production Example 1 to give 3-amino-2,4-di (4- Chloro-3-trifluoromethylphenoxy) pyridine (the present compound (45)) was obtained.

m.p. 100.5:

¹ H-NMR (300 MHz; CDC 1 TMS) δ (pm): 7.57-7.43 (m, 5H), 7.33 (dd; J = 8.7 Hz, 2.7 Hz, 1H), 7.20 (dd; J = 8.8 Hz, J = 2.8 Hz, 1H), 6.49 (d; J = 5.5 Hz, 1 H), 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)]

The same procedure was followed except that 4-promote 3-trifluoromethylphenol was used in place of 4-fluoro-3-trifluoromethylphenol in Production Example 1 to give 3-amino-1,2,4-di (4-bromo-phenol). 3-Trifluoromethylphenoxy) pyridine (the present compound (46)) was obtained.

m.p.109.6:

^{1 H-NMR (25 OMH z} ; CDC 1 3 / TMS) 6 (ppm): 7. 72 (d; J = 8.7Hz, 1H), 7.58 - 7. 43 (m, 4H), 7.26 (dd; J = 7.9 Hz, J-3.3 Hz, 1H), 7.12 (dd; J = 7.7 Hz, J = 2.6 Hz, 1H), 6.49 (d; J = 5.6 Hz, 1H), 4.06 (br.s, 2H) Production Example 1 1 [3-acetoxyacetamide-2,4 di (4-fluoro-3 — Trifluoromethylphenoxy) pyridine (a process for producing the compound (47) of the present invention)] 3-amino-1,2,4-di (4-monofluoro-3-trifluoromethylphenoxy) pyridine (0.20) g, 0.44 mmol) was dissolved in toluene (5 ml), triethylamine (45 mg, 0.45 mmol) was added, and then acetoacetic acetic chloride (54 mg, 0.39 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-acetoxyacetamide-1,2,4-di (4-fluoro-3-trifluoromethylphenoxy). ) Pyridin (the present compound (47)) 0.16 g was obtained.

m.p. 101.8

¹ H-NMR (300 MHz; CDC 1 TMS) δ (p pm): 7.92 (d; J = 5.7 Hz, 1H), 7.51 to 7.20 (m, 6H), 6.45 (d J = 5.7Hz, 1H), 4.77 (s, 2H), 2.22 (s, 3H)

Production Example 12 [3-Methoxyacetoamide-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine] (Production method of the present compound (48)) Production Example 11 The same procedure was followed except that methoxyacetic acid chloride was used instead of acetic acid chloride to obtain 3-methoxyacetamide-2,4-di (4-fluoro-3-trifluoromethylphenoxy). Pyridine (Compound (48) of the present invention) Pyridine was obtained.

m.p.120.Ot:

¹ H-NMR (300 MHz; CDC 1 TMS) δ (p pm): 7.96 (br.s, 1H), 7.91 (d; J = 5.7 Hz, 1H), 7.46- 7.20 (m, 6H), 6.45 (d; J = 5.7Hz, 1H), 4.09 (s, 2H), 3.52 (s, 3H)

Production Example 13 [3-benzylidenimino-2,4-di (4-fluoro-3-trifluoromethylphenoxy) pyridine] (Method for producing compound (49) of the present invention)

Compound (1) (0.50 g, 1.1 1 mmol) and benzaldehyde (0. (24 g, 2.22 mmol) was heated and stirred at 100 for 8 hours, and then cooled to room temperature. After the crystals have precipitated, ethanol (5 ml) is added to the mixture, and the crystals are filtered off to give 3-benzylidene imino 2,4-di (4-fluoro-mouth 3-trifluoromethylphenol). B) Pyridine (Compound (49) of the present invention) 0

• 39 g were obtained.

Yield 65%

m. p. 129.4V Examples of the compounds of the present invention are shown in Tables 1 and 2 together with the compound numbers.

Expression [I]

Compound represented by

Compound number (R ¹ ) m (R ² ) n R ³

1 3-CF ₃ , 4-F 3-CF3, 4-FH ₂

2 3-CF ₃ , 4-F 3-CF3, 4-FH

3 3-CF ₃ , 4-F 3-CF3, 4-F NHC0CF ₂ C1

_{4 3- CF 3, 4-F} 3-CF3, 4-FN (C0CH 2 0CH 3) 2

5 3-CF ₃ , 4-F 3-CF3, 4-F NHC0CH ₃

6 3-CF3, 4-F 3-CF3, 4-F NHC0CH ₂ CH ₃

7 3-CF ₃ , 4-F 3-CF3 '4-F NHCOCF3

8 3-CF ₃ , 4-F 3-CF3, 4-F NHC0CF ₂ CF ₃

9 3-CF ₃ , 4-F 3-CF ₃ , 4-FN (C0CH ₂ CH ₃ ) C0C0 ₂ CH ₃

1 0 3-CF ₃ , 4-F 3-CF ₃ , 4-FN (C0CH ₂ CH ₃ ) C0CH ₂ 0CH ₃

1 1 3-CF ₃ , 4-F 3-CF3, 4-FN (COCH ₃ ) ₂

1 2 3-CF ₃ , 4-F 3-CF3, 4-F 咖 CH ₂ CH ₃ ) ₂

1 3 3-CF ₃ , 4-F 3-CF3, 4-FN (C0CH ₂ CH ₃ ) COCH3

1 4 3-CF ₃ , 4-F 3-CF3, 4-FN (C0CH ₂ CH ₂ CH ₃ ) C0CH ₂ CH ₃

1 5 3-CF ₃ , 4-F 3-CF3, 4-FN (C0CH ₂ CH ₂ CH ₃ ) C0CH ₃

1 6 3-CF ₃ , 4-F 3-CF3, 4-F NHC0CH ₂ OCH3

1 7 3-CF ₃ , 4-F 3-CF3, 4-F NHC0CH (C1) CH ₃

1 8 3-CF ₃ , 4-F 3-CF3, 4-F Australia CH ₂ CH ₃ ) CH ₂ OCOCH3

1 9 3-CF ₃ , 4-F 3-CF3, 4-FN (COCH ₂ CH ₃ ) COCH ₂ OCH ₂ CH ₃

2 0 3-CF ₃ , 4-F 3 "CF ₃ , 4-FN (C0CH ₃ ) C0CH ₂ 0CH ₃

2 1 3-CF ₃ , 4-F 3-CF3, 4-FN (C0CH ₂ CH ₃ ) C0CH _z 0CH ₂ CH ₃

_{2 2 3- CF 3, 4-} F 3-CF3, 4-FN (C0CH 2 0CH 3) CH 2 0CH 3

2 3 3-CF ₃ , 4-F 3-CF3, 4-FN (COCH ₂ OCH ₃ ) CH ₂ 0C0CH ₃

24 3-CF ₃ , 4-F 3-CF3, 4-F NHC0CH ₂ 0CH ₂ CH ₃

2 5 3-CF ₃ , 4-F 3-CF3, 4-FN (C0CH ₂ CH ₃ ) C0CH ₂ 0C0CH ₃ Table 2

Next, formulation examples are shown. In addition, parts represent parts by weight. Formulation Example 1 Compounds of the present invention (1), (2), (5), (7), (11), (15), (41) 50 parts each of (49), 3 parts of calcium ligninsulfonate Then, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are crushed and mixed well to obtain each wettable powder.

Formulation Example 2

20 parts of each of the compounds (1), (2), (5), (7), (11), (15) and (41)-(49) and 1.5 parts of sorbitan trioleate Is mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, finely pulverized by a wet pulverization method, and an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate Add 40 parts, and further add 10 parts of propylene glycol, and stir and mix to obtain each flowable preparation.

Formulation Example 3

The compounds of the present invention (1), (2), (5), (7), (11), (15), (41), 2 parts each of (49), kaolin clay 88 parts and talc 10 parts Each powder is obtained by crushing and mixing.

Formulation Example 4

5 parts of each of the compounds of the present invention (1), (2), (5), (7), (11), (15), (41) and (49), 14 parts of polyoxyethylene styrylphenyl ether, By mixing 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene well, each emulsion is obtained.

Formulation Example 5

Compounds of the present invention (1), (2), (5), (7), (11), (15), (41) 2 parts each of (49), synthetic hydrous silicon oxide 1 part, lignin sulfonic acid 2 parts of calcium, 30 parts of bentonite and 65 parts of kaolin clay are thoroughly crushed and mixed, water is added and kneaded well, and the mixture is granulated and dried to obtain each granule.

Formulation Example 6

Compounds of the present invention (1), (2), (5), (7), (11), (15), (41) 10 parts each of (49), 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt Mix 35 parts of white carbon containing and 55 parts of water, Finely pulverized by the wet pulverization method to obtain each 10% flowable product. Formulation Example 7

0.1 part of each of the compounds (1), (2), (5), (7), (11), (15) and (41)-(49) of the present invention is replaced by 5 parts of xylene and 5 parts of trichloroethane. And then mixed with 89.9 parts of deodorized kerosene to obtain 0.1% oil solution for each.

Formulation Example 8

0.1 part of each of the compounds of the present invention (1), (2), (5), (7), (11), (15), (41)-(49), 10 parts of trichloroethane and 10 parts of deodorized kerosene 59. 9 parts are mixed and dissolved, filled into an aerosol container, and a valve part is attached. Then, 30 parts of propellant (liquefied petroleum gas) is charged under pressure through the valve part to obtain each oily aerosol.

Formulation Example 9

0.2 part of each of the compounds of the present invention (1), (2), (5), (7), (11), (15), (41)-(49), xylene 5 parts, deodorized kerosene 3.8 Part and emulsifier {ATMOS 300 (registered trademark of Atlas Chemical Co.)} A mixture of 1 part and dissolution and 50 parts of pure water are filled in an aerosol container, a valve part is attached, and a propellant (liquefied) is passed through the valve part. (Petroleum and gas) 40 parts by pressure to obtain each aqueous aerosol.

Formulation Example 10

The compound of the present invention (1), (2), (5), (7), (11), (15), (41) —10 mg of each of (49) is dissolved in an appropriate amount of acetone, and 4.0 cmx A porous ceramic plate having a thickness of 4.0 cm and a thickness of 1.2 cm is impregnated to obtain each of the heat-smoking agents. Next, the usefulness of the arthropod control agent of the present invention will be described by test examples. In addition, the compound of this invention is shown by the compound number of Table 1-2. Further, comparative compounds (A) and (B) represented by the following formulas were used as comparative control compounds. These comparative compounds (A) and (B) are the compounds described in GB-1 161492.

Comparative compound (A)

Comparative compound (B) Test example 1: Acaricidal test against Tetranychusurticae

Seven days after sowing, about 20 female adult females were released to the beetle (primary leaf stage) planted in a plastic cup planted 7 days after sowing. After leaving for 1 day, the compounds of the present invention (1), (2), (5), ( 7), (11), (15), (41), (43), (45)-(49), comparative compounds (A) and (B) were obtained according to Formulation Examples 6 of each. A water dilution of the preparation (500 ppm) 2 Oml was sprayed. Fourteen days later, the number of surviving mites on the leaves of the green bean was examined, and the control rate was determined by the formula (I). As a result, all of the compounds of the present invention exhibited an effect of controlling a rate of 90% or more. On the other hand, the control rates of the comparative compounds (A) and (B) were all less than 30%.

Formula (I)

Control rate (%) = 100X {1-(number of live mites in treated area) / (number of live mites in untreated area)}

Test Example 2: Test for miticide against Dermatophagoides farinae Dermatophagoides farinae A compound of the present invention (1) was dissolved in acetone in a predetermined amount, and the solution was rounded to a diameter of 38 mm. 0.2 ml was dropped on the black paper. After air-drying, it was laid on an aluminum dish with a bottom diameter of 38 mm, and an adhesive was applied to the edges of black paper. Approximately 30 young adults of Kona-Hyouda were released on black paper and left at 25 and 65% humidity. Twenty-four hours later, the number of surviving mites was investigated, and the control rate was determined by equation (II). The results are shown in Table 3. Formula (II)

Control rate (%) = 100 X {1— (Number of living mites (Number of test mites))

Table 3

Test example 3

To the apple seedlings (approximately 6 months after sowing) planted in a plastic cup, a water dilution (20 Oppm) 2 Om 1 of each of the compounds of the present invention (1) and (11) obtained according to Formulation Example 4 was added. Each was sprayed. After air-drying, 60 first-instar larvae of Adelaidea japonicus (Ad ox phi esorana) were released on the leaves of the apple seedlings. Seven days later, the number of surviving larvae on the leaves of the apple was examined, and the control rate was determined by the following formula (IE). As a result, all of the compounds of the present invention exhibited an effect of controlling the control rate of 90% or more.

Expression (ΙΠ)

Control rate (%) = 100 X {1-(Number of surviving larvae in treated area) Z (Number of surviving larvae in untreated area)} Industrial applicability

Since the compound of the present invention has an excellent arthropod control effect, it can be used for various arthropod pest control.

Claims

1 set

[Wherein, R ¹ and R ² are the same or different and each is a halogen atom or C 1 -C 4 haloalkyl

Represents a kill group, and n and m are the same or different and represent an integer of 1 to 3. However, when m represents an integer of 2 or more, R ¹ is the same and 3 may be different, and n is 2 or more

Five

When representing an integer, R ² may be the same or different.

R ³ is a hydrogen atom, formula NR ⁴ R ⁵ {where R ⁴ and R ⁵ are the same or different and are a hydrogen atom, a CI—C4 alkyl group, a C 2—C 5 alkoxyalkyl group, a C 3—C 4 Nyloxyalkyl group, C (= 〇) R ⁶ (R ⁶ is C 1 -C 4 alkyl group, C 1 -C 4 haloalkyl group, C 2 -C 4 alkoxyalkyl group, C 2 -C 4 alkoxy carbonyl group or C3- C4 represents Al force Noi Ruo alkoxyalkyl group) or ^{^{N = CR 7 R 8 (R}} 7 represents a hydrogen atom or a C 1 one C 4 alkyl group, R ⁸ Table of C 1-C4 alkoxy group Substituted with a halogen atom, a CI-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkyl group, a C1-C4 haloalkoxy group, a methylenedioxy group, or a C1-C4 alkylthio group Represents a good phenyl group). ]

A pyridine compound represented by the formula:

2. When the haloalkyl group is a trifluoromethyl group, a chlorodifluoromethyl group, a dichlorofluoromethyl group, a perfluoroethyl group, a perfluoropropyl group or a

-The pyridine compound according to claim 1, which is a fluorobutyl group.

3. An arthropod control agent comprising the pyridine compound according to claim 1 as an active ingredient, and further comprising a carrier.

4. An arthropod control agent comprising the pyridine compound according to claim 2 as an active ingredient, and further comprising a carrier.

5. An arthropod control method, comprising treating an effective amount of the pyridine compound according to claim 1 in an arthropod or an arthropod habitat.

6. An arthropod control method comprising treating an effective amount of the pyridine compound according to claim 2 in an arthropod or an arthropod habitat.

7 Expression

(

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

8. The haloalkyl group is a trifluoromethyl group, a chlorodifluoromethyl group, a dichlorofluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, or a perfluorobutyl group. Pyridine compound.