JP3074664B2 - Aralkyloxypyrimidine derivatives, their preparation and pesticides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel aralkyloxypyrimidine derivative, a process for producing the same, and a pest which is useful as an insecticide, acaricide, fungicide, nematocide and the like containing the same as an active ingredient. It is to provide a controlling agent.

[0004]

Means for Solving the Problems The present inventors have studied to solve the above problems, and as a result, a novel aralkyloxypyrimidine derivative is useful as an insecticide, acaricide, fungicide, nematocide, and the like. The present invention was found to have remarkable pest control activity as a pesticidal agent, and 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 lower acyloxy group or a hydroxyl group; R ² represents a halogen atom or a lower alkyl group; R ³ represents a hydrogen atom, a lower alkyl group or a halogen atom; An aralkyloxypyrimidine derivative represented by the following formula:
It is about. In the compound (I) of the present invention,
The carbon atom marked with * and the carbon atom when A is a branched alkylene are asymmetric carbon atoms, and each 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 and R ² have the same meanings as described above; X represents a halogen atom) and a pyrimidine derivative represented by the following formula (III):

[0009]

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Wherein the aralkyloxypyrimidine derivative represented by the formula (I) is reacted with an aralkyl alcohol represented by the formula (I) wherein R ³ and A are as defined above. It relates to the manufacturing method.

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

Hereinafter, the present invention will be described in detail. A novel aralkyloxypyrimidine derivative (I) which is the above-mentioned target compound [compounds (I-1), (I-2), (I-3), (I-
4) and (I-5)], and the compound (I
R ¹ , R ² , R ³ , R ⁴ , A,
M and X are as follows.

Examples of R ¹ include a halogen atom, a lower acyloxy group and a hydroxyl group. Examples of the halogen atom in 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.

The lower acyloxy group for R ¹ includes, for example, those having a straight-chain or branched alkyl group having 1 to 6 carbon atoms; Four are good (for example,
Acetyloxy group, propionyloxy group, n-butyroyloxy group, i-butyroyloxy group, etc.); more preferably, acetyloxy group.

Examples of R ² include a lower alkyl group and a halogen atom. The lower alkyl group for R ² includes, for example, a linear or branched one having 1 to 6 carbon atoms; preferably a lower alkyl group having 1 to 4 carbon atoms (for example, , Methyl, ethyl, n-propyl, i-propyl, n-
Butyl group, i-butyl group, etc.); more preferably, methyl group and ethyl group. Examples of the halogen atom for R ² include those described for R ¹ ; a chlorine atom is preferred.

Examples of R ³ include a hydrogen atom, a lower alkyl group and a halogen atom. As the lower alkyl group for R ³ , for example, those having 1 to 1 carbon atoms
There can be mentioned 6 straight-chain or branched ones; preferably 1 to 4 carbon atoms (for example, those described above as R ² ); more preferably t -A butyl group is preferred. Examples of the halogen atom for R ³ include those described above as R ¹ ; a chlorine atom and a fluorine atom are preferred.

The lower alkylene group for A may be, for example, a linear or branched one having 1 to 6 carbon atoms; preferably 1 to 4 carbon atoms.
(Eg, methylene group, ethylene group, 1
-Methylmethylene group, propylene group, butylene group, etc.); more preferably, methylene group and ethylene group.

R ⁴ and X are a halogen atom (for example, R
¹ represents those described above). M represents an alkali metal. R ⁵ represents a lower acyloxy group (lower aliphatic carboxylic acid residue) corresponding to R ¹ .

As a preferred embodiment for producing the aralkyloxypyrimidine 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):

[0020]

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(Wherein R ² , R ³ and A have the same meanings as described above; R ⁴ represents a halogen atom) and an aralkyloxypyrimidine derivative represented by the following formula (IV):

[0022]

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[0023] (wherein, R ⁴ represents. A lower acyloxy group) represented by lower aliphatic carboxylic acids and R ¹ is a lower acyloxy group in the formula (I) of the, wherein the reacting represented by For producing aralkyloxypyrimidine derivatives. [Synthesis method 3] The following formula (I-2):

[0024]

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

[0026]

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

[0028]

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

[0030]

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(Wherein, M has the same meaning as described above.)
A method for producing an aralkyloxypyrimidine derivative represented by the above formula (I), wherein R ¹ is a fluorine atom.

The synthesis of the compound (I) of the present invention will be 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.

[0033]

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(In the formula, R ¹ , R ² , R ³ , A 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; diethyl ether,
Ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; methanol, ethanol, n-propanol, i-
Alcohols such as propanol; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile; triethylamine, pyridine;
Organic bases such as N, N-dimethylaniline and the like;
3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; a mixture of the above-mentioned 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.

[0040]

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(Wherein 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 compound (VIII-1) is used in an amount of 0.5 to 3 moles, preferably 0.5 to 1.7 moles, based on 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.

[0043]

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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. Examples of the compound (II) include compounds (II-1) to (II-9) shown in Table 1 described below.

The compound (III) used in the present invention is, for example,
J. Am. Chem. Soc. 47, p. 1778 (1925), etc., according to the following formula.

[0046]

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(Wherein R ³ has the same meaning as described above;
R ⁶ represents a hydrogen atom or a methyl group; A ′ represents a direct bond or a methylene group. Examples of the compound (III) include, for example, a compound (III) [compound (I) comprising the types of substituents corresponding to compounds 1 to 30 and the like shown in Tables 2 to 5 described below.
II) ₁ to (III) ₃₀ . For example, compound (III)
_{In 1} , R ^{3 in the} formula represented by the compound (III) is a hydrogen atom, and A is a methylene group. ].

Examples of the compound (I) include the compounds 1 to 30 shown in Tables 2 to 5 described below [Compound 1 is represented by R ^{1 in the} formula represented by the compound (I).
And R ² is a chlorine atom, R ³ is a hydrogen atom, and A is an ethylene group. ].

(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.

[0050]

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(In the formula, R ² , R ³ , R ⁴ , R ⁵ and A 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 2 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.

As the compound (I-2), for example, the compounds 2,6,10,14,18,2 shown in Tables 2 to 5 described later
Compound (I-2) [Compound (I-2) ₂ , (I-2) ₆ , (I-2) ₁₀ , (I-
2) ₁₄ , (I-2) ₁₈ , (I-2) ₂₂ , (I-2) _26, etc.
For example, in the compound (I-2) ₂ , R ¹ (R ⁵ in the compound (I-2)) in the formula represented by the compound (I) is an acetyloxy group, R ² is a chlorine atom, R ³ is a hydrogen atom, A is an ethylene group. ].

(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.

[0057]

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(In the formula, R ² , R ³ , R ⁵ , A and M 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 within a temperature range from room temperature to the boiling point of the solvent to be used, and
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, compounds 3, 7, 11, 15, 19, 2 shown in Tables 2 to 5 below.
Each compound (I-3) consisting of each type of substituent corresponding to 3, 27, etc. [Compound (I-3) ₃ , (I-3) ₇ , (I-3) ₁₁ , (I-3)
₁₅ , (I-3) ₁₉ , (I-3) ₂₃ , (I-3) _{27 and the} like. For example, in the compound (I-3) ₃ , R ^{1 in the} formula represented by the compound (I) is a hydroxyl group, R ² is a chlorine atom, R ³ is a hydrogen atom, A
Is an ethylene group. ].

(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.

[0064]

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(Wherein R ² , R ³ and A 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.

[0067]

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For example, diethylaminosulfur trifluoride (DAST) and the like 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 used, and preferably from ice-cooling to 40 ° 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.

(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.

[0071]

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(In the formula, R ² , R ³ , R ⁴ , A and M 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 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 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, compounds 4,8,12,16,20,2 shown in Tables 2 to 5 below.
Compound (I-4) consisting of each type of substituent corresponding to 4, 28, 30, etc. [Compound (I-4) ₄ , (I-4) ₈ , (I-4) ₁₂ , (I
-4) ₁₆ , (I-4) ₂₀ , (I-4) ₂₄ , (I-4) ₂₈ , (I-4) _{30 and the} like. For example, in the compound (I-4) ₄ , R ^{1 in the} formula represented by the compound (I) is a fluorine atom, R ² is a chlorine atom,
R ³ is a hydrogen atom and A is an ethylene group. ].

The pests which are effective in controlling the compound (I) of the present invention include agricultural and horticultural pests [for example, Hemiptera (hoppers, leafhoppers, aphids, whiteflies, etc.), and lepidoptera (catworms). , 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 and nematicidal effect and contains at least one compound (I) as an active ingredient. Compound (I) can be used alone,
Usually, a carrier, surfactant, dispersant, adjuvant, etc. are blended by a usual method (for example, prepared as a composition such as powder, emulsion, fine granule, granule, wettable powder, oily suspension, aerosol, etc.) Is preferably used.

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, etc.) 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, improvement of absorption, and dispersion, emulsification and spreading of drugs, include, for example, 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 agent can be used alone or in an appropriate combination depending on 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.

[0082]

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. 229-231 ° C. ¹ H-NMR (CDCl ₃ , δ ppm) 1.64-1.81 (dd, 3H), 5.84-6.
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) Synthesis of 6- (1-chloroethyl) -4-chloro-5-methylpyrimidine [compound (II-8)] 4-chloro-6-ethyl5-methylpyrimidine (5.0
g) in dichloromethane (50 ml),
While heating to 5 ° C., chlorine gas was blown in for 2 hours while stirring. Nitrogen gas was blown into the reaction solution to remove dissolved chlorine gas. Next, the solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography (Wakogel C-200, eluted with toluene) to obtain 3.2 g of the target compound as a colorless oily liquid.

(Physical properties) ¹ H-NMR (CDCl ₃ , δ ppm) 1.90 to 1.95 (d, 3H), 2.50 (s, 3)
H) 5.20-5.30 (q, 1H), 8.84
(S, 1H)

(7) Synthesis of 6- (1-chloroethyl) -4-chloro-5-methylpyrimidine [compound (II-9)] 4-chloro-6-ethyl5-propylpyrimidine (1
0.0g) in dichloromethane (100ml)
The mixture was heated to 30 to 35 ° C., and chlorine gas was blown therein for 2 hours while stirring. Nitrogen gas was blown into the reaction solution to remove dissolved chlorine gas. Next, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to column chromatography (Wakogel C-20).
(0, toluene elution) to give 9.0 g of the target compound as a colorless oily liquid.

(Physical properties) ¹ H-NMR (CDCl ₃ , δ ppm) 1.02 to 1.12 (t, 3H), 1.50 to 1.82
(Multi, 2H) 1.90-1.95 (d, 3H), 2.78-2.86
(T, 2H), 5.22-5.32 (q, 1H), 8.
87 (s, 1H)

(8) Compound (II) in Table 1 was synthesized in the same manner as in the above (1) to (7).

[0096]

[Table 1]

Example 1 [Synthesis of Compound (I)] Using the compound (II) obtained in Reference Example 1, the target compound (I) was synthesized. (1) 5-chloro-6- (1-chloroethyl) -4- (2
Synthesis of -phenylethoxy) pyrimidine (compound 1) 2-phenylethanol (2.9 g) was dissolved in dry N, N-dimethylformamide (DMF) (30 ml),
Sodium hydride (60% in oil) (0.6 g) was added and stirred for 1 hour. Then, 6- (1-chloroethyl)
After dropwise addition of -4,5-dichloropyrimidine (3.5 g), the mixture was stirred and reacted at room temperature for 4 hours. After the reaction, water (10
0 ml) was slowly added, and 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 isolated by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 20: 1) to give 1.4 g of the target compound as a colorless oil.

(Physical properties) ¹ H-NMR (CDCl ₃ , δ ppm) 1.86 (d, 3H), 3.15 (s, 3H), 4.6
6 (t, 2H), 5.50 (q, 1H), 7.20-
7.40 (multi, 5H), 8.65 (s, 1H)

(2) 6- (1-acetoxyethyl) -5
Synthesis of chloro-4- (2-phenylethoxy) pyrimidine (compound 2) Compound 1 (1.0 g) was dried in DMF (30 ml).
Then, potassium acetate (1.0 g) and potassium carbonate (0.8 g) were added, and the mixture was stirred at 60 ° C. for 4 hours. After the completion of the reaction, water (100 ml) was slowly added, 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 resulting oil was subjected to column chromatography (Wakogel C-200,
Purification with toluene: ethyl acetate = 20: 1) yielded 1.1 g of the desired product as a colorless oily liquid.

(Physical properties) ¹ H-NMR (CDCl ₃ , δ ppm) 1.55 (d, 3H), 2.15 (s, 3H), 3.1
5 (t, 2H), 4.65 (t, 2H), 6.11
(Q, 1H), 7.20 to 7.35 (multi, 5
H), 8.60 (s, 1H)

(3) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- (2-phenylethoxy) pyrimidine (compound 3) Compound 2 (4.0 g) was added to ethanol (50 ml).
And then dissolved in a 1N aqueous sodium hydroxide solution (2
5 ml) and stirred at room temperature for 4 hours. After 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 = 20: 1) to obtain 3.0 g of the target compound as a colorless oily liquid.

(4) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- (2-phenylethoxy) pyrimidine (compound 4) 6- (1-hydroxyethyl) -5-chloro-4- ( 2
-Phenylethoxy) pyrimidine (2.0 g) was dissolved in chloroform (50 ml), and diethylaminosulfate fluoride (1.4 g) was added dropwise under ice-cooling.
Stirred at room temperature for 4 hours. After the completion of the reaction, water (30 ml) was slowly added, and the target compound was extracted with toluene. 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 = 20: 1) to give 0.9 g of the desired product as a colorless oily liquid.

(5) 6- (1-acetoxyethyl) -4-
Synthesis of {2- (4-t-butylphenyl) ethoxy} -5-chloropyrimidine (compound 6) 2- (4-t-butylphenyl) ethanol (1.8 g)
Was dissolved in dry tetrahydrofuran (30 ml) and sodium hydride (60% in oil) (0.4 g) was added.
Stirred for hours. Then, 6- (1-acetoxyethyl)
After dropwise adding -4,5-dichloropyrimidine (2.4 g), the mixture was stirred at room temperature for 4 hours. After the reaction, water (100m
l) was added slowly, and the target compound 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 isolated by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 20: 1) to obtain 1.0 g of the target compound as a colorless oily liquid.

(6) 4- {2- (4-t-butylphenyl)
Synthesis of ethoxy} -5-chloro-6- (1-hydroxyethyl) pyrimidine (compound 7) 2- (4-t-butylphenyl) ethanol (0.9 g)
Was dissolved in dry tetrahydrofuran (30 ml) and sodium hydride (60% in oil) (0.2 g) was added.
Stirred for hours. Then, 4,5-dichloro-6- (1-
After (hydroxyethyl) pyrimidine (0.7 g) was added dropwise, the mixture was stirred at room temperature for 4 hours. After the reaction, water (50m
l) was added slowly, and the target compound 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 isolated by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 20: 1) to obtain 0.7 g of the target compound as a colorless oily liquid.

(7) 4- {2- (4-t-butylphenyl)
Ethoxy} -5-chloro-6- (1-fluoroethyl)
Synthesis of pyrimidine (compound 8) 2- (4-t-butylphenyl) ethanol (0.9 g)
Was dissolved in dry tetrahydrofuran (30 ml) and sodium hydride (60% in oil) (0.2 g) was added.
Stirred for hours. Then, 4,5-dichloro-6- (1-
After dropwise addition of (fluoroethyl) pyrimidine (0.7 g), the mixture was stirred at room temperature for 4 hours. After the reaction, water (50m
l) was added slowly, and the target compound 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 isolated by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 20: 1) to obtain 0.7 g of the target compound as a colorless oily liquid.

(8) 4- {2- (4-t-butylphenyl)
Synthesis of ethoxy} -6- (1-chloroethyl) -5-methylpyrimidine (compound 9) 2- (4-t-butylphenyl) ethanol (1.8 g)
Was dissolved in dry tetrahydrofuran (30 ml) and sodium hydride (60% in oil) (0.5 g) was added.
Stirred for hours. Then, 6- (1-chloroethyl) -4
After dropwise addition of -chloro-5-methylpyrimidine (1.8 g), the mixture was stirred at room temperature for 4 hours. After the reaction, water (100
ml) was added slowly, and the target compound 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 isolated by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 20: 1) to obtain 1.8 g of the target compound as a colorless oily liquid.

(9) 4- {2- (4-t-butylphenyl)
Synthesis of ethoxy} -6- (1-fluoroethyl) -5-methylpyrimidine (compound 12) The above compound 9 (1.7 g) was dried in DMF (20 ml).
And cesium fluoride (1.4 g) was added.
The mixture was stirred at 100 to 120 ° C for 6 hours. After completion of the reaction, water was added, extracted with toluene, washed with water, 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).
(0, toluene: ethyl acetate = 20: 1 elution) to obtain 1.0 g of the target compound as a colorless oily liquid. (Physical properties) ¹ H-NMR (CDCl ₃ , δ ppm) 1.30 (s, 9H), 1.62 (t, 3H), 2.2
0 (m, 3H), 3.08 (t, 2H), 4.58
(T, 2H), 5.60 to 5.96 (dq, 1H),
7.20 to 7.38 (m, 4H), 8.60 (s, 1
H)

(10) Other compounds (I) in Tables 2 to 5
Other Compounds (I) in Tables 2 to 5 were synthesized according to the methods described in the above (1) to (9). Tables 2 to 5 show the compounds synthesized as described above.

[0109]

[Table 2]

[0110]

[Table 3]

[0111]

[Table 4]

[0112]

[Table 5]

Example 2 [Preparation of preparation] (1) Preparation of granules 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 powder 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 for Conger Compound (I) prepared according to Example 2 and shown in Tables 2 to 5
Each hydration agent in water containing a surfactant (0.01%).
The solution was diluted to 0 ppm, and cabbage leaf pieces (5 × 5 cm) were immersed in each of these chemical solutions for 30 seconds, placed in each plastic cup one by one, and air-dried. Next, 10 cup moths (3rd instar larvae) were released into each of these cups, covered, and
It was left in a constant temperature room at 5 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the mortality. The insecticidal effect was evaluated in four stages (A: 100%, B: 99 to 80) depending on the range of the mortality.
%, C: 79 to 60%, D: 59% or less). Table 6 shows the results.

[0118]

[Table 6]

(2) Efficacy test against black leafhopper Compound (I) prepared according to Example 2 and shown in Tables 2 to 5
Was diluted to 300 ppm with water containing a surfactant (0.01%), and rice seedlings were immersed in each of these chemical solutions for 30 seconds, air-dried, and then inserted into respective glass cylinders. did. Next, ten black leafhoppers (fourth instar larvae) were released into each cylinder, and the plugs were porous-stoppered. After standing in a constant temperature room at 25 ° C., the number of live and dead insects was counted four days later, and the insecticidal rate was determined. The results of the evaluation of the insecticidal effect are shown in Table 7 by the four-step evaluation method described in the above (1).

[0120]

[Table 7]

(3) Efficacy test on adult female spider mite, Tetranychus urticae Compound (I) prepared according to Example 2 and shown in Tables 2 to 5
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. Evaluation of the acaricidal effect
Four stages (A: 100%, B:
99-80%, C: 79-60%, D: 59% or less). Table 8 shows the results.

[0122]

[Table 8]

(4) Control effect test 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 1.5 leaf stage Then, each wettable powder of the compound (I) shown in Tables 2 to 5 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 evaluation of the bactericidal effect was carried out in 6 stages (0: overall diseased,
1: Lesion area is about 60%, 2: Lesion area is about 40%, 3: Lesion area is about 20%, 4: Lesion area is 10%.
Hereinafter, 5: no lesion). Table 9 shows the results.

[0124]

[Table 9]

(5) Test for controlling efficacy against wheat rust (preventive effect) Wheat (cultivar: Kobushi wheat) was grown 10 per pot in a plastic flowerpot having a diameter of 6 cm. A wettable powder of compound (I) shown in Tables 2 to 5 prepared according to Example 2 was added to a surfactant (0.01
%) To 500 ppm with water containing
Sprayed at 0 ml. After spraying, cultivation was performed in a glass greenhouse for 2 days, and then a spore suspension of wheat rust (7 × 10
⁽⁴ spores / ml) was sprayed and inoculated uniformly on the plant body. After inoculation, the plants were grown for one week in a glass greenhouse, and the degree of wheat leaf rust spots on the first leaves was examined. The results of the evaluation of the bactericidal effect were evaluated according to the six-step evaluation method described in (4) above.
Shown in

[0126]

[Table 10]

[0127]

The novel aralkyloxypyrimidine derivatives of the present invention have excellent effects such as insecticidal, acaricidal and bactericidal activities.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-194417 (JP, A) JP-A-4-230670 (JP, A) JP-A-1-68362 (JP, A) JP-A-63-1988 225364 (JP, A) International Publication 92/8704 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 239/34 A01N 43/54 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] (1) The following formula: (Wherein, R ¹ represents a halogen atom, a lower acyloxy group or a hydroxyl group; R ² represents a halogen atom or a lower alkyl group; R ³ represents a hydrogen atom, a lower alkyl group or a halogen atom; A is a lower alkylene group) An aralkyloxypyrimidine derivative represented by the formula: 2. The following formula: (Wherein R ¹ and R ² are as defined in claim 1;
X represents a halogen atom. And a pyrimidine derivative represented by the following formula: (Wherein, R ³ and A have the same meanings as in claim 1)
2. The method for producing an aralkyloxypyrimidine derivative represented by the formula (I) according to claim 1, wherein the aralkyloxypyrimidine derivative is reacted with an aralkyl alcohol represented by the following formula: 3. A pest control agent comprising an aralkyloxypyrimidine derivative represented by the formula (I) according to claim 1 as an active ingredient.