JP3074657B2 - Aralkylaminopyrimidine derivatives, their preparation and pesticides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aralkylaminopyrimidine derivative which is useful as an insecticide, acaricide, fungicide and the like.

[0002]

2. Description of the Prior Art Since the aralkylaminopyrimidine derivative of the present invention is a novel compound, it is not known that it has pest control activity.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel aralkylaminopyrimidine derivative, a process for producing the same, and a pesticidal agent which is useful as an insecticide, acaricide, fungicide and the like containing the same as an active ingredient. It is to be.

[0004]

Means for Solving the Problems As a result of investigations for solving the above problems, the present inventors have found that a novel aralkylaminopyrimidine derivative is useful as a pesticide, acaricide, fungicide and the like. The present inventors have found that the agent has a remarkable controlling activity as an agent, and have completed the present invention. That is,
The present invention is as follows. The first invention provides the following formula (I):

[0005]

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(Wherein R ¹ represents a halogen atom, a hydroxyl group, a lower acyloxy group or a lower acylthio group; R ² represents a lower alkyl group or a cycloalkyl group; R ³ represents a hydrogen atom, a halogen atom, a lower alkyl group) Or a lower alkoxy group; n represents an integer of 1 to 5). In the compound (I) of the present invention, the carbon atom marked with * is an asymmetric carbon atom, and any optical isomer, racemate, diastereomer compound or a mixture thereof is included in the present invention. The second invention is based on the following formula (I
I):

[0007]

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Wherein R ¹ is as defined above;
X represents a halogen atom. ) And a pyrimidine derivative represented by the following formula (III):

[0009]

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(Wherein R ² , R ³ and n have the same meanings as described above), and are reacted with an aralkylamine represented by the above formula (I). The present invention relates to a method for producing an aminopyrimidine derivative.

The third invention relates to a pesticidal composition comprising an aralkylaminopyrimidine derivative represented by the above formula (I) as an active ingredient.

Hereinafter, the present invention will be described in detail. The novel aralkylaminopyrimidine derivatives (I) [including the compounds (I-1) to (I-4)] which are the above-mentioned target compounds, and R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , n, M and X are as follows.

Examples of R ¹ include a halogen atom, a hydroxyl group, a lower acyloxy group and a lower acylthio group. Examples of the halogen atom for R ¹ include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably a chlorine atom and a fluorine atom.

As the lower acyloxy group for R ¹ , those having a total of 2 to 9 carbon atoms having a linear or branched alkyl group (for example, acetyloxy group, ethyloxy group, n-propionyloxy group, i-type) -Propionyloxy group, n-butyroyloxy group, i-butyroyloxy group, n-pentanoyloxy group, n-hexanoyloxy group, etc., and a cycloalkyl group having 4 to 9 carbon atoms (for example, cycloalkyl) Propanecarbonyloxy group, cyclopentanecarbonyloxy group, etc.)
And the like; preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms in total, and a cycloalkyl group having 3 to 4 carbon atoms in total; More preferred are acetyloxy, ethyloxy, n-pentanoyloxy, cyclopropanecarbonyloxy and the like.

The lower acylthio group for R ¹ includes:
Total number of carbon atoms having a linear or branched alkyl group of 1
To 4 (eg, acetylthio, ethylthio, n-propionylthio, i-propionylthio, n-butyroylthio, i-butyroylthio), and the like; Good.

Examples of R ² include a lower alkyl group and a cycloalkyl group. As the lower alkyl group for R ^{2, a} linear or branched one having 1 to 6 carbon atoms (for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, -Butyl group, t-butyl group, pentyl group, hexyl group, etc.), and the like;
Four are preferred; methyl and ethyl are more preferred.

As the cycloalkyl group for R ² ,
Examples thereof include those having 3 to 8 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like); preferably those having 3 to 5 carbon atoms; Preferably, a cyclopropyl group is good.

R ³ is a hydrogen atom, a halogen atom,
Examples thereof include a lower alkyl group and a lower alkoxy group.

Examples of the halogen atom for R ³ include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably a chlorine atom and a fluorine atom.

Examples of the lower alkyl group for R ³ include straight-chain or branched ones having 1 to 6 carbon atoms; preferably those having 1 to 4 carbon atoms (for example, , A methyl group, an ethyl group, an n-propyl group,
i-propyl, n-butyl, i-butyl, t-butyl and the like); and more preferably a methyl group.

As the lower alkoxy group for R ³ ,
Examples thereof include linear or branched ones having 1 to 6 carbon atoms; preferably those having 1 to 4 carbon atoms (e.g., methoxy, ethoxy, n-propoxy, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, etc.); and more preferably methoxy group.

R ⁴ and X are a halogen atom (eg, R
¹ represents those described above). R ⁵ is R
^{It represents} a lower acyloxy group (lower aliphatic carboxylic acid residue), a lower acylthio group (lower fatty acid thiocarboxylic acid residue), etc. corresponding to ¹ . M represents an alkali metal.

As n, an integer of 1 to 5 can be exemplified. The relationship between n and R ³ is as follows. When R ³ is a hydrogen atom, n represents 5. When R ³ is a halogen atom, a lower alkyl group or a lower alkoxy group, n
Represents an integer of 1 to 5; in the case of a lower alkyl group or a lower alkoxy group, n is preferably 1; and in the case of a halogen atom, n is preferably 1, 2 or 5. And (R
³ ) The substitution position of _n is not particularly limited; when R ³ is a lower alkyl group or a lower alkoxy group, the 4-position is preferable; when R ³ is a halogen atom, 2, 3, 4,
The 5,6 and / or 4-position is preferred.

As can be understood from the compound (I) of the present invention, the compound (I) has an amino group and can easily form an acid addition salt. Included in the invention. Examples of the acid forming an acid addition salt include inorganic acids (hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, etc.), carboxylic acids (formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid) , Aconitic acid, etc.), organic sulfonic acids (methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), saccharin and the like.

As a preferred embodiment for producing the aralkylaminopyrimidine derivative represented by the above formula (I), in addition to the synthesis method 1 described as the second invention,
The following four types of production methods (synthesis methods 2 to 5) can be exemplified. [Synthesis method 2] The following formula (I-1):

[0026]

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Wherein R ² , R ³ and n are as defined above; R ⁴ represents a halogen atom; and an aralkylaminopyrimidine derivative represented by the following formula (IV):

[0028]

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(Wherein R ⁵ represents a lower acyloxy group or a lower acylthio group). In the above formula (I), R ¹ is a lower aliphatic carboxylic acid. The present invention relates to a method for producing an aralkylaminopyrimidine derivative represented by an acyloxy group or a lower acylthio group. [Synthesis method 3] The following formula (I-2):

[0030]

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(Wherein R ² , R ³ , R ⁵ and n have the same meanings as described above) and an aralkylaminopyrimidine derivative represented by the following formula (V):

[0032]

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(Wherein M represents an alkali metal). An aralkylaminopyrimidine derivative represented by the above formula (I) wherein R ¹ is a hydroxyl group is reacted with an inorganic base represented by the formula: It concerns the manufacturing method. [Synthesis Method 4] The following formula (I-3):

[0034]

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Wherein R ² , R ³ and n have the same meanings as described above, and the aralkylaminopyrimidine derivative represented by the formula (I) is reacted with a fluorinating agent. The present invention relates to a method for producing an aralkylaminopyrimidine derivative in which R ¹ is a fluorine atom. [Synthesis Method 5] An aralkylaminopyrimidine derivative represented by the above formula (I-1) and the following formula (VI):

[0036]

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Wherein M represents an alkali metal. The aralkylaminopyrimidine derivative represented by the above formula (I), wherein R ¹ is a fluorine atom, is reacted with a fluorine compound represented by the formula (I). It concerns the manufacturing method.

The synthesis of the compound (I) of the present invention is described in more detail by the following synthesis methods 1 to 5. (Synthesis Method 1) The synthesis of compound (I) of the present invention can be usually carried out by reacting compound (II) as a raw material with compound (III) in a solvent or without solvent as shown below. Although it is possible, the reaction is preferably performed in the presence of a base in order to accelerate the reaction.

[0039]

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(Wherein R ¹ , R ² , R ³ , n and X have the same meanings as described above). The solvent is not particularly limited as long as it does not directly participate in the reaction. Chlorinated or unchlorinated aromatics, such as benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane, Aliphatic or alicyclic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; ketones, such as acetone, methyl ethyl ketone, etc .; N, N-dimethylformamide, N, N-dimethylacetamide, etc. Amides such as acetonitrile and propionitrile What nitriles; triethylamine, pyridine, N,
Organic bases such as N-dimethylaniline; 1,3-
Dimethyl-2-imidazolidinone; dimethyl sulfoxide; a mixture of the above solvents, and the like.

The amount of the solvent used depends on the amount of the compound (I
The compound (I) can be used in a concentration range of 5 to 80% by weight, but it is preferable to use the compound (II) in a concentration of 10 to 70% by weight.

The base is not particularly limited.
Organic bases (eg, triethylamine, pyridine, N,
N-dimethylaniline, DBU, etc.), alkali metal alkoxides (eg, sodium methoxide, sodium ethoxide, etc.), inorganic bases (eg, sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate, hydrogen carbonate) Sodium, potassium carbonate, etc.); and organic bases are preferred.

The amount of the base used is the same as that of the compound (I
It can be used in a molar amount of 0.001 to 5 times, preferably 0.8 to 5 times the molar amount of I).
The reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent to be used or lower, and is preferably from 80 to 110 ° C.

The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 0.3 to 2 hours. The amount of the starting compound used is the compound (II) with respect to the compound (II).
I) is 0.5 to 2 moles, preferably 0.8 to 2 moles.
The molar ratio is preferably 1.5 times.

The compound (II) (when R ¹ = X) used in the present invention is usually prepared by reacting the starting compound (VII-
It can be produced by reacting 1) with compound (VIII-1) in a solvent.

[0046]

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(Wherein, when R ¹ = X, X has the same meaning as described above.) Examples of the solvent include those described above; ) Can be used in a concentration range of 5 to 80% by weight. The reaction temperature is not particularly limited, but the reaction can be carried out in a temperature range from room temperature to the boiling point of the solvent used or lower. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 2 to 10 hours.

The amount of the starting compound to be used is 0.5 to 3 times, preferably 0.5 to 1.7 times, the molar amount of the compound (VIII-1) to the compound (VII-1). Is good. Compound
(VII-3) is described, for example, in Journal of Chemical Society (JCS) 3478-3481 (195).
According to the method described in (5 years), it can be produced as shown in the following formula.

[0049]

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(Wherein X is as defined above; R
May optionally have a lower alkyl group, a hydrogen atom, a hydroxyl group or a halogen atom. ) After completion of the reaction, the target compound (II) produced as described above is extracted, concentrated,
Perform normal post-treatments such as filtration, recrystallization,
It can be appropriately purified by known means such as various types of chromatography. As the compound (II), for example, Table 1
Compounds (II-1) to (II-7) shown therein can be exemplified.

Compound (III) used in the present invention is, for example,
J. Am. Chem. Soc. 54, 3441 (1932); Am. Chem. Soc. , 61
Volume, p. 1321, (1939), etc., according to the following formula.

[0052]

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(Wherein R ² , R ³ and n have the same meanings as described above).
Compounds (III) [Compounds (III) ₁ to (III)] consisting of the types of substituents corresponding to compounds 1 to 30 shown in 6, etc.
Called ₃₀ . For example, the compound (III) ₁ is the same as the compound (I
In the formula shown in II), it means that R ² is a methyl group and R ³ is a hydrogen atom. ].

Compounds (I) include, for example, those described in Tables 2 to 6
Compounds 1 to 30 [compound 1 is compound (I)
R in the formula represented by¹Is a chlorine atom, R^TwoIs methyl
Group, R ^ThreeIs a hydrogen atom. ]
be able to.

(Synthesis Method 2) Compound (I-2) [Compound (I)
In which R ¹ is a lower acyloxy group] can be usually carried out by reacting compound (I-1) with compound (IV) in a solvent or without solvent, but the reaction is accelerated. For this reason, the reaction is preferably performed in the presence of a base.

[0056]

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(In the formula, R ² , R ³ , R ⁴ , R ⁵ and n have the same meanings as described above.) As the solvent, in addition to the solvent described in Synthesis Method 1, acetic acid, propionic acid, etc. And a mixture thereof; N, N-dimethylformamide and the same aliphatic carboxylic acid as the acyloxy group to be introduced are preferred.

The amount of the solvent used depends on the amount of the compound (I-
The compound (I) can be used such that the concentration of 1) is in the range of 5 to 80% by weight. Preferably, the compound (I-1) is used in a concentration of 10 to 70% by weight. Good. Examples of the base include the bases described in Synthesis method 1; and inorganic bases are preferred.

The amount of the base used is the same as that of the compound (I-
1) can be used at 1 to 5 times the molar amount of
Preferably, it is 2 to 5 moles. The reaction temperature is
Although not particularly limited, it is in the temperature range from room temperature to the boiling point of the solvent to be used or lower, and preferably 80 to 120 ° C.

The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 10 to 50 hours. As the compound (IV), a commercially available product can be used. After completion of the reaction, the target compound (I-2) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and, if necessary, to a known process such as recrystallization or various types of chromatography. It can be appropriately purified by means.

Compounds (I-2) include, for example, those described in Tables 2 to 6
Compounds 2,7,11 to 15,20,23,2 shown therein
Each compound consisting of each type of substituent corresponding to 6 and the like (I-
2) (Compound (I-2)_Two , (I-2)₇, (I-2)₁₁~ (I-2)
 ₁₅, (I-2)₂₀, (I-2)_{twenty three}, (I-2) ₂₆And so on. example
If this compound (I-2)_TwoIs a compound represented by the formula (I)
R in¹[R in compound (I-2)^FiveIs acetyl
Oxy group, R^TwoIs a methyl group, R^ThreeIs a hydrogen atom
Means ].

(Synthesis Method 3) Compound (I-3) [Compound (I)
Wherein R ¹ is a hydroxyl group,
The reaction can be carried out by reacting compound (I-2) with compound (V) in a solvent in the presence of a base.

[0063]

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(In the formula, R ² , R ³ , R ⁵ , M and n have the same meanings as described above.) As the solvent, in addition to the ethers, ketones and amides described in Synthesis Method 1, , Alcohols (eg, methanol, ethanol, propanol, butanol, etc.), water, and mixtures of the above-mentioned solvents; preferably, mixtures of alcohols and water. The amount of the solvent used is determined by the amount of the compound (I
The compound (I-2) may be used such that the concentration of the compound (I-2) is 10 to 70% by weight. Is good.

Examples of the base include the inorganic bases described in Synthesis Method 1; sodium hydroxide and potassium hydroxide are preferred. The base can be used in an amount of 1 to 5 moles, preferably 2 to 5 moles, per 1 mole of the compound (I-2).

The reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent to be used or lower.
50 ° C. is preferred. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 0.5 to 1 hour.

As the compound (V), a commercially available product can be used. The target compound (I-
After completion of the reaction, 3) is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and can be appropriately purified as necessary by known means such as recrystallization and various types of chromatography.

Compounds (I-3) include, for example, those described in Tables 2 to 6
Each compound (I-3) consisting of each type of substituent corresponding to compounds 3, 8, 16, 27, etc. shown therein [Compound (I-3)
₃ , (I-3) ₈ , (I-3) ₁₆ , (I-3) _27, etc. For example, the compound (I-3) ₃ means that R ^{1 in the} formula represented by the compound (I) is a hydroxyl group, R ² is a methyl group, and R ³ is a hydrogen atom. ].

(Synthesis Method 4) Compound (I-4) [Compound (I)
In which R ¹ is a fluorine atom] can be usually produced by reacting compound (I-3) with a fluorinating agent in a solvent or without solvent.

[0070]

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(In the formula, R ² , R ³ and n have the same meanings as described above.) As the solvent, the chlorinated or non-chlorinated aromatic, aliphatic or alicyclic ring described in Synthesis Method 1 is used. Mention may be made of hydrocarbons of the formula, ethers and mixtures of said solvents.

The amount of the solvent used is determined by the amount of the compound (I-
The compound (I-3) can be used in a concentration range of 5 to 80% by weight, but it is preferable to use the compound (I-3) in a concentration of 10 to 70% by weight. Good. Examples of the fluorinating agent include fluorinated alkylaminosulfurs.

[0073]

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For example, diethylaminosulfur trifluoride (DAST) shown below can be used. Then, the amount of use is 1 to compound (I-3).
Although it can be used in a molar amount of 5 times, it is preferably 1 to 2 times.

The reaction temperature is not particularly limited, but is in the range of from the ice-cooling temperature to the boiling point of the solvent to be used, preferably from ice-cooling to room temperature. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 0.3 to 2 hours.

(Synthesis Method 5) Compound (I-4) [Compound (I)
In which R ¹ is a fluorine atom] is synthesized by reacting compound (I-1) with compound (VI) [fluorine compound] in a solvent or without solvent, in addition to synthesis method 4. Can also be done.

[0077]

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(In the formula, R ² , R ³ , R ⁵ , M and n have the same meanings as described above.) Examples of the solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide. And 1,3-dimethyl-2-imidazoline;
Dimethyl sulfoxide; sulfolane; a mixture of the above solvents, and the like.

The amount of the solvent used is determined by the amount of the compound (I-
The compound (I) can be used such that the concentration of 1) is in the range of 5 to 80% by weight. Preferably, the compound (I-1) is used in a concentration of 10 to 70% by weight. Good. Examples of the compound (VI) include an alkali metal fluorine compound, preferably cesium fluoride,
Potassium fluoride is good.

The compound can be used in an amount of 1 to 5 moles, preferably 1.2 to 3 moles, based on Compound (I-1). It is good. The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent to be used, and 100 to 140.
C is preferred.

The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 1 to 8 hours. After completion of the reaction, the target compound (I-4) produced by Synthetic methods 4 and 5 is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, recrystallization, various chromatography, and other known methods. Can be appropriately purified by the above-mentioned means.

Compounds (I-4) include, for example, those described in Tables 2 to 6
Compounds 4, 9, 17, 21, 21, 24, 28 to 3 shown in
Each compound consisting of each type of substituent corresponding to 0 or the like (I-
4) [Compound (I-4) ₄ , (I-4) ₉ , (I-4) ₁₇ , (I-4) ₂₁ , (I
-4) ₂₄ and (I-4) ₂₈ to (I-4) ₃₀ . For example, the compound (I-4) ₄ means that R ^{1 in the} formula represented by the compound (I) is a fluorine atom, R ² is a methyl group, and R ³ is a hydrogen atom. ].

Examples of the pests which can be controlled by the compound (I) of the present invention include agricultural and horticultural pests [eg, Hemiptera (Cyberidae, leafhoppers, aphids, whiteflies, etc.), and Lepidoptera (Cycoridae) , Scarabaeidae, Coleoptera, Pestiformes, Scarabaeidae, Pieris beetle, etc., Coleoptera (Tenebrionidae, Weevils, Chrysomelidae, Scarabaeidae, etc.), Acari (Acari: Tetranychidae, Tetranychidae, etc.) )], Sanitary pests (for example, flies, mosquitoes, cockroaches, etc.), stored grain pests (e. G. For example, wheat rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato Epidemics, etc.) can be mentioned.

The pesticidal composition of the present invention has a remarkable insecticidal property.
It has an acaricidal / bactericidal effect and contains at least one compound (I) as an active ingredient. Compound (I)
Can be used alone, but usually, a carrier, a surfactant, a dispersant, an auxiliary agent, etc. are blended by a conventional method (for example, powders, emulsions, fine granules, granules, wettable powders, oil-based Prepared as a composition such as a suspension or an aerosol).

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 Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection), and the like.

Surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, absorption, and 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 preparation, the above-mentioned carrier, surfactant, dispersant and auxiliary can be used alone or in appropriate combination according to the respective purposes.
When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in the emulsion, and usually from 0.3 to 0.3 in the 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.

[0088]

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 (II)] (1) Synthesis of 6- (1-chloroethyl) -4,5-dichloropyrimidine [Compound (II-1)] 4,5-dichloro-6-ethylpyrimidine (270 g) )
Is dissolved in dichloromethane (750 ml) and 30-35
C., and chlorine gas was blown in for 2 hours while stirring. Nitrogen gas was blown into the reaction solution to remove dissolved excess chlorine gas. Then, the solvent was distilled off under reduced pressure, and the obtained residue was distilled under reduced pressure to obtain 240 g of the target substance as a pale yellow liquid.

(2) Synthesis of 4,5-dichloro-6- (1-fluoroethyl) pyrimidine [compound (II-4)] 6- (1-hydroxyethyl) -4,5-dichloropyrimidine (2.1 g) ) Was dissolved in dichloromethane (15 ml), diethylaminosulfur trifluoride (2.0 g) was added dropwise under ice cooling and stirring, and the mixture was further stirred at room temperature for 1 hour to complete the reaction. Cold water (20 ml) was added to the reaction solution, the dichloromethane layer was separated, washed with water, and dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure,
The obtained residue was purified by column chromatography (Wakogel C-200, eluted with chloroform) to obtain 1.3 g of the target substance as a pale yellow oily liquid.

(Physical properties) b. p. 229 ° to 231 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm 1.64 to 1.81 (dd, 3H), 5.84 to 6.
19 (dq, 1H), 8.92 (s, 1H)

(3) 5-chloro-4-fluoro-6- (1
-Fluoroethyl) pyrimidine [Compound (II-5)] Synthesis of 4,5-dichloro-6- (1-fluoroethyl) pyrimidine (1.3 g) with N, N-dimethylformamide (1
0 ml) and cesium fluoride (4.0 g)
Was added and stirred at room temperature for 1.5 hours to complete the reaction. Cold water (10 ml) was added to the reaction solution, and the separated oil was extracted with toluene, washed with water and dried over anhydrous sodium sulfate.
Then, the solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography (Wakogel C-200, elution with chloroform) to obtain 1.0 g of the target substance as a pale yellow oily liquid.

(Physical properties) b. p. 192 to 194 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm 1.66 to 1.82 (dd, 3H), 5.85 to 6.
21 (dq, 1H), 8.83 (s, 1H)

(4) 6- (1-acetoxyethyl) -4,
Synthesis of 5-dichloropyrimidine [compound (II-6)] 6- (1-chloroethyl) -4,5-dichloropyrimidine (10.2 g) was converted to N, N-dimethylformamide (1
50 ml), potassium acetate (12.0 g) and potassium carbonate (3.0 g) were added, and the mixture was stirred at about 60 ° C. for 3 hours. Water (200 ml) was added to the reaction solution, and the separated oil was extracted with toluene, washed with water and dried over anhydrous sodium sulfate. Next, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to column chromatography (Wakogel C-20).
0, toluene: ethyl acetate = 10: 1 elution) to obtain 5.2 g of the target substance as a pale yellow liquid.

(Physical properties) ¹ H-NMR (CDCl ₃ ) δ ppm 1.55 to 1.62 (d, 3H), 2.15 (s, 3)
H), 6.00 to 6.12 (q, 1H), 8.84
(S, 1H)

(5) Synthesis of 4,5-dichloro-6- (1-hydroxyethyl) pyrimidine [compound (II-7)] 6- (1-acetoxyethyl) -4,5-dichloropyrimidine (4.0 g) ) In tetrahydrofuran (50 ml)
In 1N aqueous sodium hydroxide solution (3.
0 ml) was slowly added dropwise. After the addition, the mixture was further stirred at room temperature for 1 hour to complete the reaction. Next, the desired product was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 5: 1) to obtain 2.8 g of the target substance as a pale yellow liquid.

(Physical properties) ¹ H-NMR (CDCl ₃ ) δ ppm 1.47 to 1.52 (d, 3H), 3.76 to 3.85
(D, 1H), 5.17-5.25 (m, 1H), 8.
88 (s, 1H)

(6) Compound (II) was synthesized in the same manner as in the above (1) to (5).

[0098]

[Table 1]

Example 1 [Synthesis of Compound (I)] Using Compound (II) obtained in Reference Example 1, the intended compound (I) was synthesized. (1) 6- (1-chloroethyl) -5-chloro-4- (α
-Methyl-4-phenoxybenzylamino) pyrimidine (Compound 1) Synthesis of α-methyl-4-phenoxybenzylamine (9.0
g) and triethylamine (12.0 g) were dissolved in toluene (50 ml), and 6- (1-chloroethyl)-
4,5-Dichloropyrimidine (10.1 g) was added and 5
Heated to reflux for an hour. After completion of the reaction, the solvent was distilled off under reduced pressure, the desired product was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C).
(-200, eluted with toluene) to obtain 8.6 g of the desired product as a colorless oily liquid.

(2) 6- (1-acetoxyethyl) -5
Synthesis of chloro-4- (α-methyl-4-phenoxybenzylamino) pyrimidine (compound 2) 5-chloro-6- (1-chloroethyl) -4- (α-methyl-4-phenoxybenzylamino) pyrimidine (7 0.5 g) in DMF (50 ml) and then
Potassium acetate (10.6 g) and potassium carbonate (3.0
g) and stirred at 50-60 ° C. for 10 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, water was added, and the desired product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C).
-200, toluene: ethyl acetate = 10: 1 elution) to give 5.5 g of the target compound as a colorless oily liquid.
g was obtained.

(3) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- (α-methyl-4-phenoxybenzylamino) pyrimidine (compound 3) 6- (1-acetoxyethyl) -5 Chloro-4- (α
-Methyl-4-phenoxybenzylamino) pyrimidine (5.0 g) was dissolved in ethanol (150 ml), and a 1N aqueous sodium hydroxide solution (50 ml) was added.
Stir at room temperature for 3 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, and the desired product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 10: 1) to obtain 5.5 g of the target compound as a colorless oil.

(4) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- (α-methyl-4-phenoxybenzylamino) pyrimidine (compound 4) 5-chloro-6- (1-hydroxyethyl ) -4- (α
-Methyl-4-phenoxybenzylamino) pyrimidine (2.0 g) was dissolved in dichloromethane (30 ml),
Under ice-cooling, diethylaminosulfur trifluoride (1.0 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, ice water (30 ml) was added, and the desired product was extracted with chloroform. The extract was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oil was subjected to column chromatography (Wakogel C-20).
The residue was purified by eluting with 0: toluene: ethyl acetate = 20: 1 to give 1.2 g of the target compound as a colorless oily liquid.

(5) Synthesis of 5-chloro-6- (1-chloroethyl) -4- {α-ethyl-4- (4-fluorophenoxy) benzylamino} pyrimidine (compounds 5 and 6) α-ethyl-4 -(4-Fluorophenoxy) benzylamine (2.0 g) was dissolved in ethanol (30 ml), and 6- (1-chloroethyl) -4,5-dichloropyrimidine (1.9 g) was added. Stirred for hours. After completion of the reaction, the solvent was distilled off under reduced pressure, water was added, and the desired product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, eluted with toluene: n-hexane = 5: 1) to give 0.8 g of the desired product as a colorless oil and its isomer, colorless. 0.
5 g were obtained.

(6) 6- (1-acetoxyethyl) -5
Chloro-4- {α-cyclopropyl-4- (4-fluorophenoxy) benzylamino} pyrimidine (Compound 1
Synthesis of 1) α-cyclopropyl-4- (4-fluorophenoxy)
Benzylamine (2.6 g) and triethylamine (1.
5 g) was dissolved in toluene (30 ml).
-(1-Acetoxyethyl) -4,5-dichloropyrimidine (2.4 g) was added, and the mixture was heated under reflux for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, water was added, and the desired product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-
200, toluene: ethyl acetate = 10: 1 elution) to give 3.8 g of the target substance as a colorless viscous substance.
Obtained.

(7) 5-chloro-4- {α-cyclopropyl-4- (4-fluorophenoxy) benzylamino}
-6- (1-hydroxyethyl) pyrimidine (compound 1
Synthesis of 6) α-cyclopropyl-4- (4-fluorophenoxy)
Benzylamine (2.6 g) and triethylamine (1.
5 g) in toluene (30 ml) and then
4,5-Dichloro-6- (1-hydroxyethyl) pyrimidine (1.9 g) was added, and the mixture was heated under reflux for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, water was added, and the desired product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C).
-200, toluene: ethyl acetate = 10: 1 elution) to give 3.5 g of the target substance as a colorless viscous substance.
g was obtained.

(8) 5-chloro-4- {α-cyclopropyl-4- (4-fluorophenoxy) benzylamino}
-6- (1-Fluoroethyl) pyrimidine (Compound 1
Synthesis of 7) α-cyclopropyl-4- (4-fluorophenoxy)
Benzylamine (2.6 g) and triethylamine (1.
5 g) in toluene (30 ml) and then
4,5-Dichloro-6- (1-fluoroethyl) pyrimidine (2.0 g) was added, and the mixture was heated under reflux for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, water was added, and the desired product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-
200, toluene: ethyl acetate = 20: 1 elution) to give 3.5 g of the target substance as a colorless viscous substance.
Obtained.

(9) 5-chloro-4- {α-ethyl-4-
(Pentafluorophenoxy) -benzylamino} -6
Synthesis of-(1-fluoroethyl) pyrimidine (compound 19) 5-chloro-6- (1-chloroethyl) -4- {α-ethyl-4- (pentafluorophenoxy) benzylamino} pyrimidine (1.2 g) It was dissolved in toluene (15 ml), cesium fluoride (2.4 g) was added, and the mixture was stirred at about 60 ° C. for 10 hours. After completion of the reaction, water was added, and the desired product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, toluene: ethyl acetate = 40: 1 elution) to obtain 0.8 g of a colorless viscous target compound.

(10) Synthesis of other target compound (I) in Tables 2 to 6 According to the method described in the above (1) to (9), other target compound (I) in Tables 2 to 6 Was synthesized. Tables 2 to 6 show the compounds synthesized as described above.

[0109]

[Table 2]

[0110]

[Table 3]

[0111]

[Table 4]

[0112]

[Table 5]

[0113]

[Table 6]

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, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium ligninsulfonate were uniformly mixed, then kneaded by adding a small amount of water, and then granulated and dried 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) Name; manufactured by Kao Corporation)
Then, it was pulverized to obtain a wettable powder.

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

(4) Preparation of dust 5 parts by weight of compound 1, 50 parts by weight of talc and kaolin 4
5 parts by weight were uniformly mixed to obtain a powder.

Example 3 [Efficacy test] (1) Efficacy test against Spodoptera litura Compound (I) prepared according to Example 2 and shown in Tables 2 to 6
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 effect was evaluated in four stages (A: 100%, B: 99-80%, C: 7) according to the range of the insecticidal rate.
9 to 60%, D: 59% or less). Table 7 shows the results.

[0119]

[Table 7]

(2) Efficacy test on brown planthopper Compound (I) prepared according to Example 2 and shown in Tables 2 to 6
Each hydration agent in water containing a surfactant (0.01%).
After dilution to 0 ppm, 30
After immersion for 2 seconds and air-drying, it was inserted into each glass cylinder. Next, ten brown planthoppers (4th instar larvae) were released into each of these glass cylinders, covered with a porous lid, and allowed to stand in a constant temperature room at 25 ° C. After 4 days, the number of live and dead insects in each glass cylinder was counted. Mortality was determined. The results of the evaluation of the insecticidal effect
Table 8 shows the four-step evaluation method described in (1).

[0121]

[Table 8]

(3) Efficacy test on adult female spider mite (Acari: Tetranychidae) Compound (I) prepared according to Example 2 and shown in Tables 2 to 6
Each hydration agent in water containing a surfactant (0.01%).
Each bean leaf (20 m in diameter) diluted to 0 ppm and infested with 10 adult female spider mites in each of these solutions
m) for 15 seconds. Next, each leaf piece was left in a constant temperature room at 25 ° C., and after 3 days, the number of live and dead insects in each leaf piece was counted to determine the acaricidal rate. The results of the evaluation of the acaricidal effect were evaluated in four stages (A: 100) according to the range of the acaricidal rate.
%, B: 99-80%, C: 79-60%, D: 59%
Below). Table 9 shows the results.

[0123]

[Table 9]

(4) Test for controlling efficacy against cucumber downy mildew (preventive effect) One cucumber (cultivar: Sagami Hanshiro) 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 compound (I) shown in Tables 2 to 6 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%), and Sprayed with 20 ml. After spraying, cultivate in a glass greenhouse for 2 days, then prepare zoosporangium of cucumber downy mildew from diseased leaves,
This was spray-inoculated evenly on the back of the plant leaf. After the inoculation, the mixture was 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 evaluation of the bactericidal effect was performed in six stages (0: the whole diseased, 1: the lesion area was about 60%, 2: the lesion area was about 40%, and 3: (Lesion area is about 20%, 4: Lesion area is 10% or less, 5: No lesion). Table 10 shows the results.

[0125]

[Table 10]

(5) Test for controlling efficacy against barley powdery mildew (preventive effect) 10 barleys (cultivar: black wheat) are grown in plastic flower pots having a diameter of 6 cm per pot, and seedlings at the 1.5 leaf stage Then, each wettable powder of the compound (I) shown in Tables 2 to 6 prepared according to Example 2 was added to a surfactant (0.01%)
And diluted with water containing 500 ppm to each, and each of these chemicals was sprayed at 20 ml per pot. These were cultivated in a glass greenhouse for 2 days, and then barley powdery mildew spores were collected from the diseased leaves and sprinkled evenly over each plant for inoculation. Next, these were grown in a glass greenhouse for one week, and the degree of barley powdery mildew spots that appeared on each first leaf was investigated. The results of the evaluation of the bactericidal effect
The results are shown in Table 11 by the six-step evaluation method described in the above (4).

[0127]

[Table 11]

[0128]

Industrial Applicability The novel aralkylaminopyrimidine derivative of the present invention has an excellent pest control effect on insecticide, acaricide, sterilization and the like.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-230670 (JP, A) JP-A-1-68362 (JP, A) JP-A-63-225364 (JP, A) International Publication 92/8704 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 239/42 A01N 43/54 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] (1) The following formula: (Wherein, R ¹ represents a halogen atom, a hydroxyl group, a lower acyloxy group or a lower acylthio group; R ² represents a lower alkyl group or a cycloalkyl group; R ³ represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group) An aralkylaminopyrimidine derivative represented by the following formula: wherein n represents an integer of 1 to 5. 2. The following formula: (Wherein, R ¹ has the same meaning as described in claim 1; X represents a halogen atom.) And a pyrimidine derivative represented by the following formula: (Wherein R ² , R ³ and n have the same meanings as described in claim 1), and are reacted with an aralkylamine represented by the formula (I). Process for producing aralkylaminopyrimidine derivatives. 3. A pest control agent comprising an aralkylaminopyrimidine derivative represented by the formula (I) according to claim 1 as an active ingredient.