JPH11116555A - 4-anilinopyrimidine derivative and insecticidal, acaricidal and microbicidal agent containing the same and useful for agriculture and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new derivative useful as an insecticide, an acaricide, a microbicide and the like. SOLUTION: A compound of formula I [R<1> is H, a 1-4C alkyl, a halogen; R<2> is H, a 1-4C haloalkyl or the like; R<3> is H, a 2-5C acyl or the like; Ar is (substituted) phenyl, naphthyl or the like; (n) is 1-3]. For example, 6-(3- trifluoromethyl-4-fluoroanilino)pyrimidine. The compound of formula I is obtained by reacting a compound of formula II (X is a halogen) with a compound of formula III in the presence of a base in a solvent, reacting the obtained intermediate of formula IV with a compound of the formula: HO-Ar in the presence of a base in a solvent, and subsequently reacting the obtained reaction product with a compound of the formula: R<3> -X in the presence of a base in a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to 4-anilinopyrimidine derivatives useful as insecticides, acaricides, fungicides and the like.

[0002]

2. Description of the Prior Art Anilinopyrimidine derivatives are described, for example, in JP-T-7-508999 as useful as insecticides and acaricides. However, the disclosed compound is only a specific 4,6-dianilinopyrimidine, and there is no specific disclosure of the 4-anilinopyrimidine derivative as in the present invention. Furthermore, this 4,6-
Dianilinopyrimidine is not practical because it has weak effects as an insecticide, acaricide and fungicide.
Further, Japanese Patent Application Laid-Open No. 9-506363 discloses a 4,6-dianilinopyrimidi derivative, and describes its use as a tyloxykinase inhibitor.
-There is no specific disclosure of the anilinopyrimidine derivative, and there is no description on its effect as an insecticide, acaricide and fungicide.

[0003]

An object of the present invention is to provide novel 4-anilinopyrimidine derivatives and 4-anilinopyrimidine derivatives useful as insecticides, acaricides, fungicides and the like.

[0004]

The present inventors have conducted studies to solve the above-mentioned problems. As a result, the present inventors have found that a novel 4-anilinopyrimidine derivative has excellent control as an insecticide, acaricide, fungicide and the like. They have found that they have activity, and have completed the present invention. That is, the present invention is as follows. First
The invention of the following formula (1):

[0005]

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Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom;
² represents a hydrogen atom, 1-4 haloalkoxy group carbon atoms, a phenoxy group, a halogen atom, C 1 -C 4 alkyl groups or 1 to 4 carbon atoms haloalkyl group; R ³ Represents a hydrogen atom, an acyl group having 2 to 5 carbon atoms or an alkyl group having 1 to 4 carbon atoms; Ar
Represents an unsubstituted or substituted halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a phenoxy group, an alkoxy group having 1 to 4 carbon atoms, Represents a phenyl group, a naphthyl group or a methylenedioxyphenyl group having 1 to 4 alkylthio groups or a haloalkoxy group having 1 to 4 carbon atoms; n represents an integer of 1 to 3; )) Is concerned with the 4-anilinopyrimidine derivative. The second invention relates to an insecticide, acaricide, and fungicide for agricultural and horticultural use containing a 4-anilinopyrimidine derivative represented by the above formula (1) as an active ingredient.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. R ^{1 to} R ³ , Ar, n represented by the novel 4-anilinopyrimidine derivative as the target compound and its production raw material
And X are as follows. [R ¹ ] Examples of R ¹ include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom.
Examples of the alkyl group include a linear or branched alkyl group, and preferably CH3. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; preferably, a chlorine atom.

[R ² ] R ² is a hydrogen atom, a haloalkoxy group having 1 to 4 carbon atoms, a phenoxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a carbon atom having 1 to 4 carbon atoms. Haloalkyl groups;
Preferably, when n = 1, hydrogen atom and carbon atom number 1
A haloalkyl group having 1 to 4 carbon atoms, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and when n = 2, a haloalkyl group having 1 to 4 carbon atoms or / and a halogen atom. The position of the substituent is not particularly limited; however, it is preferably at the 3- or 4-position. The number 1-4 haloalkoxy group carbon atoms, there may be mentioned those which have been linear or branched substituted with 1-5 halogen atoms; preferably CF ₃ O. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like; preferably, a fluorine atom and a chlorine atom. The alkyl group having 1 to 4 carbon atoms, there may be mentioned a straight or branched; preferably, is CH _3. Examples of the haloalkyl group having 1 to 4 carbon atoms include straight-chain or branched ones substituted with 1 to 5 halogen atoms; preferably, CF ₃ .

[R ³ ] Examples of R ³ include a hydrogen atom, an acyl group having 2 to 5 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Examples of the acyl group having 2 to 5 carbon atoms include a linear or branched fatty acid residue; preferably, CH ₃ CO, C ₂ H ₅ C
O, it is a n-C ₃ H ₇ CO. The alkyl group having 1 to 4 carbon atoms, there may be mentioned a straight or branched; preferably, is CH _3.

[Ar] Examples of Ar include a phenyl group, a naphthyl group and a methylenedioxyphenyl group. The phenyl group is a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a phenoxy group, an alkoxy group having 1 to 4 carbon atoms, It can have an alkylthio group having 1 to 4 atoms, a haloalkoxy group having 1 to 4 carbon atoms, and the like. The positions of these substituents are not particularly limited; however, they are preferably at positions 3 and 4. Examples of the halogen atom include the aforementioned halogen atoms; preferably, a fluorine atom, a chlorine atom and a bromine atom. Examples of the haloalkyl group having 1 to 4 carbon atoms include straight-chain or branched ones substituted with 1 to 5 halogen atoms;
₃

As an alkyl group having 1 to 6 carbon atoms
Can be straight-chain or branched;
Preferably, C_TwoH_Five, T-C_FourH₉It is. Carbon atom
As the alkoxy groups having 1 to 4 groups, straight-chain or branched
But preferably CH 2_ThreeO
It is. As a haloalkoxy group having 1 to 4 carbon atoms
Is a linear or branched group substituted with 1 to 5 halogen atoms.
A branch-like one; preferably, CF
_ThreeO. An alkylthio group having 1 to 4 carbon atoms
Can be linear or branched
Preferably; n-C_ThreeH₇S. [N] n can be an integer of 1 to 3
Is preferably 1 or 2. [X] X includes the halogen atoms described above.
But preferably a chlorine atom or a bromine atom.

As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned, and preferable compounds from the viewpoint of efficacy are as follows. Compound (1)
Examples thereof include those obtained by combining the above-described various substituents. Preferred examples from the viewpoint of the efficacy are as follows. (1) R ¹ and R ³ are hydrogen atoms, (R ² ) n is a haloalkyl group having 1 to 4 carbon atoms and a halogen atom, and Ar is a halogen atom and a haloalkyl having 1 to 4 carbon atoms. A phenyl group having a group as a substituent. (2) R ¹ , (R ² ) n and R ³ are hydrogen atoms, and Ar
Is a phenyl group having a halogen atom and a haloalkyl group having 1 to 4 carbon atoms as substituents. (3) R ¹ and R ³ are hydrogen atoms, (R ² ) n is a haloalkyl group having 1 to 4 carbon atoms and a halogen atom, and Ar substitutes an alkyl group having 1 to 6 carbon atoms. A phenyl group as a group. (4) R ¹ and R ³ are hydrogen atoms, (R ² ) n is a haloalkyl group having 1 to 4 carbon atoms and a halogen atom, and Ar is a phenyl group having a halogen atom as a substituent. . (5) R ¹ and R ³ are hydrogen atoms, (R ² ) n is a haloalkyl group having 1 to 4 carbon atoms and a halogen atom, and Ar is an alkylthio group having 1 to 4 carbon atoms. A phenyl group as a group.

(6) R ¹ and R ³ are hydrogen atoms, and (R
² ) n is a haloalkyl group having 1 to 4 carbon atoms and a halogen atom, and Ar is a halogen atom and a phenyl group having the same or different halogen atom as a substituent. (7) R ¹ and R ³ are hydrogen atom, (R ²⁾ n is 1-4 haloalkyl group and a halogen atom carbon atom and Ar is a naphthyl group. (8) R ¹ and R ³ are hydrogen atom, (R ²⁾ n is 1-4 haloalkyl group and a halogen atom carbon atom and Ar is a methylenedioxyphenyl group. (9) R ¹ and R ³ are hydrogen atoms, (R ² ) n is a haloalkyl group having 1 to 4 carbon atoms and a halogen atom, and Ar is a haloalkyl group having 1 to 4 carbon atoms. A phenyl group as a group. (10) R ¹ is a hydrogen atom, and (R ² ) n is 1 carbon atom
A to four haloalkyl group and a halogen atom, R ³
Is an acyl group having 2 to 5 carbon atoms, and Ar is a phenyl group having a halogen atom and a haloalkyl group having 1 to 4 carbon atoms as substituents. (11) R ¹ and R ³ are hydrogen atoms, (R ² ) n is a haloalkyl group having 1 to 4 carbon atoms and a halogen atom, and Ar is a haloalkoxy group having 1 to 4 carbon atoms. A phenyl group having a substituent. (12) R ¹ is a hydrogen atom, and (R ² ) n is 1 carbon atom
A to four haloalkyl group and a halogen atom, R ³
Is an alkyl group having 1 to 4 carbon atoms, and Ar is a phenyl group having a halogen atom and a haloalkyl group having 1 to 4 carbon atoms as substituents.

The compound (1) can be synthesized by the following Production Method 1 or Production Method 2. [Production Method 1] As shown below, a compound (4) which is an intermediate is obtained by reacting a commercially available compound (2) and a compound (3) in a solvent in the presence of a base. The target compound (1-1) can be produced by reacting (5) with a solvent in the presence of a base.
Then, the target compound (1-2) can be produced by reacting the commercially available starting compound (7) with a solvent in the presence of a base.

[0015]

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Wherein R ^{1 to} R ³ , Ar, n and X are
It is the same as the above. The type of the solvent in the reaction for obtaining the intermediate compound (4) is not particularly limited as long as it does not directly participate in the reaction. For example, benzene, toluene, xylene,
Chlorinated or unchlorinated aromatic, aliphatic and cycloaliphatic carbons such as methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane Hydrogens; ethers such as diethyl ether, tetrahydrofuran, dioxane and the like; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N, N-
Amides such as dimethylacetamide; nitriles such as acetonitrile, propionitrile; alcohols such as methanol, ethanol, propanol, butanol; triethylamine, pyridine;
Organic bases such as N, N-dimethylaniline and the like;
3-dimethyl-2-imidazolidone; dimethyl sulfoxide; a mixture of the above-mentioned solvents, and the like.

The amount of the solvent used is such that the compound (3) is 2-80.
% By weight;
20% by weight is preferred. The type of the base is not particularly limited, and examples thereof include aniline, triethylamine, pyridine, N, N-dimethylaniline, and the same as compound (3).
Organic bases such as DBU, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, sodium hydride, sodium amide, sodium hydroxide,
Inorganic bases such as potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate and the like can be mentioned; however, the same organic bases as aniline and triethylamine as compound (3) are preferable. The amount of the base to be used is 1 to 10 moles compared to compound (3); preferably 1 to 5 moles. The reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower;
100 ° C. is preferred. The reaction time varies depending on the above concentration and temperature; it is usually 1 to 10 hours. The amount of compound (3) used is the same as that of compound (2)
Is 1 to 2 moles, preferably 1 to 1.2 moles.

The type of the solvent in the reaction for obtaining the compound (1-1) from the compound (4) is not particularly limited as long as it does not directly participate in the reaction. For example, the above-mentioned solvents can be suitably used. The amount of the solvent used is as follows.
Can be used up to 80% by weight;
3-20% by weight is preferred. The type of the base is not particularly limited, and the above-mentioned bases can be suitably used, but an inorganic base such as potassium carbonate is preferable. The amount of the base to be used is 1- to 10-fold the molar amount of compound (5); The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent used or less;
00-120 ° C is preferred. The reaction time depends on the concentration,
Depends on temperature; usually 1 to 8 hours.

[Production Method 2] As shown below, a commercially available compound (2) and compound (5) are reacted in a solvent in the presence of a base to obtain an intermediate compound (6). The target compound (1-1) can be produced by reacting with a commercially available compound (3) in a solvent in the presence of a base. Then, the target compound (1-2) can be produced by reacting the commercially available starting compound (7) with a solvent in the presence of a base.

[0020]

Embedded image

Wherein R ^{1 to} R ³ , Ar, n and X are
It is the same as the above. The type of the solvent in the reaction for obtaining the intermediate compound (6) is not particularly limited as long as it does not directly participate in the reaction. For example, the above-mentioned solvents can be suitably used. The compound (5) can be used in an amount of 2 to 80% by weight; however, 3 to 20% by weight is preferable. The type of base is not particularly limited, and the above-mentioned bases can be suitably used; however, inorganic bases such as potassium carbonate are preferable.

The reaction temperature is not particularly limited, but is in the range of from room temperature to the boiling point of the solvent used or less;
~ 120 ° C is preferred. The amount of the base used is the same as that of compound (5)
1 to 5 moles, preferably 1 to 2 moles. The reaction time varies depending on the above concentration and temperature; it is usually 1 to 8 hours. The type of the solvent in the reaction for obtaining the compound (1-1) from the compound (6) is not particularly limited as long as it does not directly participate in the reaction. For example, the above-mentioned solvents can be suitably used. The amount can be used such that the amount of the compound (6) is 2 to 80% by weight; however, 3 to 20% by weight is preferable. The type of the base is not particularly limited, and the above-mentioned bases can be suitably used; however, the same organic bases as aniline and triethylamine as compound (3) are preferable. The amount of base used is
It is 1 to 5 moles compared to Compound (3); preferably 1 to 2 moles.

The reaction temperature is not particularly limited, but is in the range of from room temperature to the boiling point of the solvent used or less;
~ 130 ° C is preferred. The reaction time varies depending on the above concentration and temperature; it is usually 1 to 8 hours. further,
The target compound (1-2) can be produced by reacting a commercially available starting compound (7) with a solvent in the presence of a base in the same manner as in the production method (1). After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, by known means such as recrystallization and various types of chromatography. It can be appropriately purified. Examples of the compound (1) include the compounds shown in Tables 1 to 4 described below.

The compounds (1) of the present invention which have a controlling effect include agricultural and horticultural insect pests (for example, Hemiptera (hoppers, leafhoppers, aphids, whiteflies, etc.), lepidoptera (armyworms, Diamondback moths, snails,
Species, stag beetles, cabbage beetles, etc., Coleoptera (Tenebrionidae, weevil, etc.), Acarinae (eg, red mites of the spider mite family, red spider mites, etc.),
Sanitary pests (for example, flies, mosquitoes, cockroaches, etc.), grain storage pests (e.g., black beetles, beetles, etc.), and wood pests (for example, termites such as house termites, Yamato termites, terrestrial termites, leaf beetles, beetles, sink beetles) , Beetles, bark beetles, etc.), root-knot nematodes, pine wood nematodes, and mite in soil, and also pathogenic fungi such as wheat rust, barley powdery mildew,
Cucumber downy mildew, rice blast, tomato late blight, etc.).

The agricultural and horticultural insecticides, acaricides and fungicides of the present invention contain at least one compound (1) as an active ingredient. The compound (1) can be used alone as the compound (1), but is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent, and the like by a conventional method (for example,
Powders, emulsions, fine granules, granules, wettable powders, oily suspensions, aerosols and the like). Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons (benzene) , Toluene, xylene, etc.),
Chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohol (E.g., methanol, n-hexanol, ethylene glycol, etc.), polar solvents (e.g., dimethylformamide, dimethyl sulfoxide), liquid carriers such as water; gaseous carriers such as air, nitrogen, carbon dioxide, freon (in this case, mixed injection) Can be used).

Examples of surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement in absorption, dispersion, emulsification and spreading of drugs, include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent.

In the preparation of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary can be used alone or in appropriate combination, respectively, according to the respective purposes.
When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in an emulsion, and usually 0.3% in a powder.
25 to 25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. is there. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0028]

EXAMPLES The present invention will be specifically described below with reference examples and examples. Note that these examples do not limit the scope of the present invention. Reference Example 1 [Synthesis of Compound (4)] (1) 6-chloro-4- (3-trifluoromethyl-4-
Synthesis of (fluoroanilino) pyrimidine 4,6-dichloropyrimidine (3.0 g), 3-trifluoromethyl-4-fluoroaniline (3.6 g) and triethylamine (3.3 g) were added to ethanol (30 m
1) and refluxed for 10 hours. Then, water was added thereto, and the separated oil was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The resulting residue was subjected to column chromatography (Wakogel C-200, ethyl acetate: toluene = 1: 1).
5 elution) to obtain the target product (3.0 g) as pale yellow platelet-like crystals. m. p. 159 to 161 ° C

Reference Example 2 [Synthesis of Compound (6)] (1) 6-chloro-4- (3-trifluoromethyl-4-
Synthesis of Fluorophenoxy) pyrimidine 4,6-Dichloropyrimidine (6.0 g) was dissolved in dimethyl sulfoxide (100 ml), potassium carbonate (6.3 g) was added, and the mixture was heated to 40 to 50 ° C. and stirred with heating.
Trifluoromethyl-4-fluorophenol (7.2
g) in dimethyl sulfoxide (50 ml) was added dropwise. After the completion of the dropwise addition, a stirring reaction was performed at the same temperature for 4 hours. Then, water was added thereto, and the separated oil was extracted with ethyl acetate.
The extract was washed with water and dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained residue was purified by column chromatography (Wakogel C-200, eluted with toluene) to give colorless plate crystals. An object (11.5g)
I got m. p. 57-58 ° C

(2) Synthesis of 6-chloro-4- (3-trifluoromethyl-4-fluorophenoxy) -5-methylpyrimidine 4,6-dichloro-5-methylpyrimidine (2.4 g)
And 3-trifluoromethyl-4-fluorophenol (1.8 g) were dissolved in dimethyl sulfoxide (30 ml), and potassium carbonate (2.0 g) was added.
For 8 hours. Then, water was added thereto, and the separated oil was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure.
The obtained residue was purified by column chromatography (Wakogel C-200, eluted with toluene) to give the target compound (2.7 g) as colorless crystals. m. p. 93-94 ° C

Reference Example 3 [Synthesis of compound N0.9 disclosed in Japanese Patent Publication No. 7-508999] (1) 4,6-bis (3-trifluoromethylanilino)
Synthesis of pyrimidine 4,6-dichloropyrimidine (2.0 g) and 3-trifluoromethylaniline (6.5 g) were prepared at 100 to 120 ° C.
For 6 hours. Then, water was added thereto, and the separated oil was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The resulting residue was subjected to column chromatography (Wakogel C).
-200, eluting with ethyl acetate: toluene = 1: 4) to give the desired product (1.1 g) as pale brown crystals.

M. p. 187 to 191 ° C ¹ H-NMR (CDCl ₃ , δ value, ppm) 6.30 (s, 1H), 7.21 to 7.28 (m, 3
H), 7.41-7.49 (m, 3H), 7.78-
7.90 (m, 4H), 8.41 (s, 1H)

Example 1 [Synthesis of Compound (1)] (1) Synthesis of 6- (3-trifluoromethyl-4-fluorophenoxy) -4- (3-trifluoromethyl-4-fluoroanilino) pyrimidine Synthesis of [Compound 1] 6
-Chloro-4- (3-trifluoromethyl-4-fluorophenoxy) pyrimidine (1.5 g) and 3-trifluoromethyl-4-fluoroaniline (1.8 g) were added to 10
The mixture was stirred and reacted at 0 to 130 ° C. for 6 hours. After the reaction was completed, water was added, and the separated oil was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The obtained residue was subjected to column chromatography (Wakogel C-200, ethyl acetate: toluene =
1: 3 elution) to obtain the target product (1.3 g) as colorless plate-like crystals. m. p. 105-108 ° C

(2) 6- (4-fluorophenoxy) -4
-(3-trifluoromethyl-4-fluoroanilino)
Synthesis of Pyrimidine [Compound 8] Synthesis of 6-chloro-4- (3-trifluoromethyl-4-fluoroanilino) pyrimidine (0.5 g) and 4-fluorophenol (0.2) in dimethyl sulfoxide (10 m
l), add potassium carbonate (0.4 g) and add
The mixture was stirred and reacted at １００100 ° C. for 3 hours. After the reaction was completed, water was added, and the separated oil was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The resulting residue was subjected to column chromatography (Wakogel C-200, ethyl acetate: toluene = 1: 1).
9 elution) to obtain the desired product (0.56 g) as pale yellow powdery crystals. m. p. 135-137 ° C

(3) Synthesis of N-acetyl-6- (3-trifluoromethyl-4-fluorophenoxy) -4- (3-trifluoromethyl-4-fluoroanilino) pyrimidine Synthesis of Compound 21 -(3-Trifluoromethyl-4-fluorophenoxy) -4- (3-trifluoromethyl-4-fluoroanilino) pyrimidine (1.7 g) is dissolved in terahydrofuran (50 ml), and sodium hydride ( 60% in-oil
1.0 g) and stirred at room temperature for 1 hour. Then, acetyl chloride (1.0 g) was added, and the mixture was stirred at 50 to 60 ° C for 4 hours. After the reaction was completed, water was added, and the separated oil was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The obtained residue was subjected to column chromatography (Wakogel C-gel).
200, ethyl acetate: toluene = 1: 10 elution) to obtain the target compound (1.0 g) as colorless powdery crystals. m. p. 94-97 ° C ¹ H-NMR (CDCl ₃ , δ value, ppm) 2.10 (s, 3H), 7.18-7.62 (m, 7
H), 8.41 (m, 1H)

(4) Synthesis of N-methyl-6- (3-trifluoromethyl-4-fluorophenoxy) -4- (3-trifluoromethyl-4-fluoroanilino) pyrimidine [Synthesis of Compound 24] 6 -(3-Trifluoromethyl-4-fluorophenoxy) -4- (3-trifluoromethyl-4-fluoroanilino) pyrimidine (1.0 g) and potassium hydroxide (0.2 g) were added to acetone (30 ml). Dissolve and stir at room temperature for 1 hour. Then, methyl iodide (1.0 g) was added, and the mixture was stirred at 50 to 60 ° C for 4 hours. After the reaction was completed, water was added, and the separated oil was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The obtained residue was subjected to column chromatography (Wakogel C-200, ethyl acetate: toluene =
(1:10 elution) to give the desired product (0.8 g) as pale yellow powdery crystals. m. p. 94 to 97 ° C ¹ H-NMR (CDCl ₃ , δ value, ppm) 3.48 (s, 3H), 7.15 to 7.58 (m, 7
H), 8.35 (m, 1H)

(5) Synthesis of Other Compound (1) Compounds (1) synthesized according to the methods described in the above (1) to (4) are shown in Tables 1 to 4.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

Example 2 [Preparation of preparation] (1) Preparation of granule 5 parts by weight of compound (1), 35 parts by weight of bentonite, 57 parts by weight of talc, neoperex powder (trade name; manufactured by Kao Corporation) 1 Parts by weight and 2 parts by weight of sodium ligninsulfonate were uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound (1), 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neoperex powder (trade name, manufactured by Kao Corporation) and Demol (Trade name; manufactured by Kao Corporation)
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of emulsion Compound (1) was added to 20 parts by weight of xylene and 70 parts by weight of xylene.
10 parts by weight of Toxanone (trade name, manufactured by Sanyo Chemical Industries) was uniformly mixed and melted to obtain an emulsion.

(4) Preparation of Dust A compound (1) was uniformly mixed with 5 parts by weight, 50 parts by weight of talc and 45 parts by weight of kaolin to obtain a dust.

Example 3 [Efficacy test] (1) Efficacy test on Spodoptera litura Compounds (1) prepared according to Example 2 and shown in Tables 1 to 4
Each wettable powder was diluted to 500 ppm with water containing a surfactant (0.01%), soybean leaves were immersed in each of these chemicals for 30 seconds, placed one by one into each plastic cup, and air-dried. did. In each of these cups, ten cutworm armyworms (2nd instar larvae) were released, covered, left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate. The insecticidal rates of Compounds 1, 9, and 21 were 80% or more. Incidentally, Table 7-508 used as a control
The insecticidal rate of the compound (No. 9) disclosed in Japanese Patent Publication No. 999 was 0%.

(2) Efficacy test against Conaga (1) Compounds (1) shown in Tables 1-4 prepared according to Example 2
Was diluted to 300 ppm with water containing a surfactant (0.01%), and cabbage leaf pieces (5 × 5 cm) were immersed in each of these chemical solutions for 30 seconds, and one piece was placed in each plastic cup. One by one and air-dried. Release 10 moths (3rd instar larvae) into each of these cups, cover them, and place them at 25 ° C.
, And two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate. The insecticidal rates were determined for compounds 1,7,20,
21, 23, and 24 were 80% or more. The insecticidal rate of the compound (No. 9) disclosed in JP-T-7-508999 used as a control was 30%.

(3) Efficacy test on adult female spider mite (Acari: Tetranychidae) Compounds (1) prepared according to Example 2 and shown in Tables 1-4
Was diluted to 300 ppm with water containing a surfactant (0.01%), and each of these liquid chemicals was infested with 10 adult female spider mites, kidney beans (diameter 20 mm).
mm) for 15 seconds. Next, these leaf pieces were allowed to stand in a constant temperature room at 25 ° C., and three days later, the number of live and dead insects in each leaf piece was counted to determine the acaricidal rate. The acaricidal rate was 80% or more for compounds 1, 7, 10, 12, 15 to 25, 27. In addition, Japanese Patent Publication No. 7-50899 used as a control
The insecticidal rate of the compound (No. 9) disclosed in Japanese Patent Publication No. 9 was 0%.

(4) Rice Blast Control Effect Test (Preventive Test) Ten rice plants (variety: Nipponbare) were grown per pot in a plastic flowerpot having a diameter of 6 cm. Each wettable powder of the compound (1) shown in Tables 1 to 4 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%) and sprayed in 20 ml per pot. . After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then the leaves of the conidia of rice blast prepared from the diseased leaves were uniformly spray-inoculated onto the plant leaves. 28 days after inoculation for 5 days
The plants were grown in a moist chamber at ℃ and the degree of rice blast lesions on the leaves was investigated. As for the lesion area, compounds 1 and 7 showed 10% or less. Incidentally, Table 7-508 used as a control
The compound (N0.9) disclosed in Japanese Patent Publication No. 999 is
The whole was ill.

(5) Cucumber downy mildew control effect test (preventive test) One cucumber (cultivar: Sagami-tan white) is grown per pot in a plastic flower pot having a diameter of 6 cm, and a 1.5-leaf seedling is planted. To the body, each wettable powder of the compound (1) shown in Tables 1-4 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%), and 20 ml per pot was diluted. We sprayed one by one. Next, zoosporangium of cucumber downy mildew was prepared from the diseased leaves, and this was spray-inoculated evenly from above the plants. After the inoculation, the plants were kept in the dark at 20 ° C. for 2 days, then grown in a glass greenhouse for 5 days, and the degree of cucumber downy spots appearing on the first leaf was examined. The drug effect was compared with the degree of the lesion in the untreated plot. The lesion area was 20% or less for Compounds 1 and 2. Incidentally, Table 7
No. 508999 (N0.
9) was totally ill.

[0051]

The novel 4-anilinopyrimidine derivative of the present invention has excellent effects such as insecticidal, acaricidal and bactericidal activities.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazuyuki Nakamura 5 Ube Kogushi 1978 Kobe, Ube City, Yamaguchi Prefecture

Claims (2)

[Claims] (1) The following formula (1): (Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom; R ² represents a hydrogen atom,
A haloalkoxy group having 1 to 4 carbon atoms, a phenoxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms;
³ represents a hydrogen atom, an acyl group having 2 to 5 carbon atoms or an alkyl group having 1 to 4 carbon atoms; Ar represents an unsubstituted or substituted halogen atom, 1 to 4 carbon atoms;
Haloalkyl groups, alkyl groups having 1 to 6 carbon atoms, phenoxy groups, alkoxy groups having 1 to 4 carbon atoms, alkylthio groups having 1 to 4 carbon atoms or halo having 1 to 4 carbon atoms Represents a phenyl group, a naphthyl group or a methylenedioxyphenyl group having an alkoxy group; n represents an integer of 1 to 3. Aanilinopyrimidine derivative represented by the formula: 2. An insecticide, acaricide and fungicide for agricultural and horticultural use comprising a 4-anilinopyrimidine derivative represented by the formula (1) according to claim 1 as an active ingredient.