JP2649125B2 - Alkylaminopyrimidine derivatives, their preparation and pesticides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel alkylaminopyrimidine derivative which is useful as an insecticide, acaricide, fungicide and the like.

[0002]

2. Description of the Prior Art Since the alkylaminopyrimidine 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 alkylaminopyrimidine derivative, a process for producing the same, and a pesticidal agent containing the same as an active ingredient which is useful as an insecticide, acaricide, fungicide and the like. It is to be.

[0004]

Means for Solving the Problems As a result of investigations to solve the above problems, the present inventors have found that a novel alkylaminopyrimidine 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 or a lower acyloxy group; R ² represents an alkyl group having 1 to 12 carbon atoms; Z represents an oxygen atom or a sulfur atom;
n represents an integer of 1 to 12. )). A second invention provides the following formula (II):

[0007]

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

[0009]

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Wherein R ² , Z and n have the same meanings as described above, and an alkylamino represented by the above formula (I), which is reacted with an alkylamine represented by the above formula. The present invention relates to a method for producing a pyrimidine derivative.

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

In addition, as a preferred embodiment for producing the alkylaminopyrimidine derivative represented by the above formula (I), in addition to the synthesis method 1 described as the second invention, the following four kinds of production methods (synthesis method) 2 to 5).
The synthesis method 2 has the following formula (I = 1):

[0013]

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

[0015]

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[0016] (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 And a method for producing an alkylaminopyrimidine derivative. The synthesis method 3 has the following formula (I-2):

[0017]

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(Wherein R ² , Z and n have the same meanings as described above; R ⁴ represents a lower acyloxy group) and an alkylaminopyrimidine derivative represented by the following formula (V):

[0019]

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(Wherein M represents an alkali metal). The alkylaminopyrimidine 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.
The synthesis method 4 has the following formula (I-3):

[0021]

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Wherein R ² , Z and n are as defined above, and a fluorinating agent is reacted with the alkylaminopyrimidine derivative represented by the formula (I). And a method for producing an alkylaminopyrimidine derivative in which R ¹ is a fluorine atom. Synthetic Method 5 comprises an alkylaminopyrimidine derivative represented by the aforementioned formula (I-1) and the following formula (VI):

[0023]

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(Wherein M represents an alkali metal). The alkylaminopyrimidine 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.

Hereinafter, the present invention will be described in detail. A novel alkylaminopyrimidine derivative (I) [compounds (I-1), (I-2), (I-
3) and (I-4)], and R ¹ , R ² , R ³ ,
R ⁴ , Z, n, X and M are as follows.

Examples of R ¹ include a halogen atom, a hydroxyl group and a lower acyloxy group. Halogen atom (e.g., chlorine atom, iodine atom, bromine atom, fluorine atom) in R ¹ as is preferably a chlorine atom, a fluorine atom.

As the lower acyloxy group for R ^{1, a} linear or branched one having 1 to 4 carbon atoms (for example, acetyloxy group, n-propionyloxy group,
i-propionyloxy group, n-butyroyloxy group,
Examples thereof include an i-butyroyloxy group, a t-butyroyloxy group, and a cyclic group having 3 to 6 carbon atoms (for example, a cyclopropylcarbonyloxy group, a cyclopentylcarbonyloxy group, a cyclohexylcarbonyloxy group, and the like). An acetyloxy group, an n-propionyloxy group and a cyclopropylcarbonyloxy group are preferred.

As R ² , a linear or branched alkyl group having 1 to 12 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl) -Butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group,
Undecyl group, dodecyl group) and the like; preferably linear or branched one having 1 to 8 carbon atoms; more preferably methyl group, ethyl group,
An n-propyl group and an octyl group are preferred.

R ³ and X are each a halogen atom (eg, R
¹ as described above). M represents an alkali metal. R ⁴ represents a lower acyloxyl group (lower aliphatic carboxylic acid residue) corresponding to R ¹ . Z represents an oxygen atom or a sulfur atom. n represents an integer of 1 to 12; preferably an integer of 1 to 10; more preferably an integer of 2 to 8; more preferably 2, 3, 6 or 8.

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. In the compound (I) of the present invention, the carbon atoms marked with * are asymmetric carbon atoms, and any of the individual optical isomers, racemic compounds or mixtures thereof are included in the present invention.

The compound (I) of the present invention can be synthesized by any of the following synthesis methods 1 to 5. (Synthesis Method 1) In the synthesis of compound (I) of the present invention, as shown below, usually, starting compound (II) and compound (II)
The reaction can be carried out by reacting the compound with I) in a solvent or in the absence of a solvent. In order to accelerate the reaction, the reaction is preferably carried out in the presence of a base.

[0032]

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(In the formula, R ¹ , R ² , Z, 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 and fats, such as, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane Aromatic and 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; acetonitrile, 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 (II) can be used in such a manner that the concentration of I) is in the range of 5 to 80% by weight.
Is preferably used in such a manner that the concentration thereof becomes 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 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 to be used is 0.5 to 2 times, preferably 0.8 to 1.5 times, the molar amount of the compound (III) relative to the compound (II).

The compound (II) to be used in the present invention is usually composed of a compound (VII) as a raw material and a compound (V
And III) in a solvent.

[0039]

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(In the formula, R ¹ and X have the same meanings as described above.) Examples of the solvent include those described above; the amount of the solvent is such that the concentration of the compound (VII) is 5 to 80. weight%
Can be used. 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 is usually 2 to 1
It can be done in 0 hours.

The amount of the starting compound used is the same as that of compound (VII)
The compound (VIII) is 0.5 to 3 moles, preferably 0.5 to 1.7 moles, based on the weight of the compound (VIII).
Compound (VII) is described, for example, in Journal of Chemical Society (JCS) 3478-3481.
According to the method described in (1955), it can be produced by the following formula.

[0042]

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Wherein X is as defined above; R
Represents a hydrogen atom, a hydroxyl group or a halogen atom. The target compound (II) produced as described above is
After completion of the reaction, ordinary post-treatments such as extraction, concentration, and filtration are performed, and if necessary, purification can be appropriately performed by known means such as recrystallization and various types of chromatography. Compound (I
Examples of I) include the compounds (II-
1) to (II-7).

Compound (III) used in the present invention is described, for example, in J. Am. Am. Chem. Soc. , 54 volumes, 3441
P. (1932), J.M. Am. Chem. Soc. , 6
1, p. 1321 (1939), etc., according to the following formula.

[0045]

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(Wherein R ² , Z, X and n are as defined above). As the compound (III), for example, each of the compounds corresponding to the compounds 1 to 20 shown in Tables 2 to 4 Each compound (III) consisting of the type of the substituent [compound (III) ₁ to (III)
No. ₂₀ . For example, the compound (III) ₁ is a compound represented by the formula (III) wherein R ² is a methyl group,
It means that Z is a sulfur atom and n is 8. ].

Compounds (I) include, for example, those described in Tables 2 to 4
Compounds 1 to 20 [Compound 1 is compound (I)
In the formula, R ¹ represents a chlorine atom, R ² represents a methyl group, Z represents a sulfur atom, and n represents 8. ].

(Synthesis Method 2) The synthesis of compound (I-2) [compound wherein R ¹ in compound (I) is a lower acyloxyl group] is usually carried out by compound (I-1) and compound (I
The reaction can be carried out by reacting V) with or without a solvent, but it is preferable to carry out the reaction in the presence of a base to promote the reaction.

[0049]

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(In the formula, R ² , R ³ , R ⁴ , n and Z have the same meanings as described above.) As the solvent, in addition to the solvent described in Synthesis Method 1, acetic acid, propionic acid and the like can be used. Such aliphatic carboxylic acids, mixtures thereof and the like can be mentioned; N, N-dimethylformamide and the same aliphatic carboxylic acid as the acyloxyl 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 in such a manner that the concentration of -1) is in the range of 5 to 80% by weight.
It is preferred that the concentration of 1) is 10 to 70% by weight. 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
The compound can be used at 1 to 5 moles with respect to -1), but preferably at 1.2 to 2 moles. Although the reaction temperature is not particularly limited, it is in the temperature range from room temperature to the boiling point of the solvent to be used, 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 1 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.
If necessary, it can be appropriately purified by known means such as recrystallization and various types of chromatography.

As the compound (I-2), for example, Table 2
Each compound (I-2) [compounds (I-2) ₂ , (I-2) ₆ , and (I-2) _6] consisting of the types of the substituents corresponding to the compounds ₂ , ₆ , ₇ , ₈ , 14 and the like shown in (I-2) ₇ , (I-
2) ₈ , (I-2) _14, etc. For example, the compound (I-2) ₂ means that R ¹ (R ⁴ in the compound (I-2)) in the formula represented by the compound (I) is an acetyloxy group, Z is a sulfur atom, and n is 8. Means that. ].

(Synthesis Method 3) Compound (I-3) [compound (I) in which R ¹ is a hydroxyl group]
Usually, compound (I-2) and compound (V) in the presence of a base
And a reaction in a solvent.

[0056]

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(In the formula, R ² , R ⁴ , Z, n 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 a mixture of the above solvents can be mentioned; preferably, a mixture of alcohols and water is good. And
The amount of the solvent used is such that the concentration of the compound (I-2) is 5-8.
The compound (I-2) can be used in a concentration range of 0% by weight.
It is good to use it so that it may be 0% by weight.

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

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,
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) produced as described above
In the step (-3), after the completion of the reaction, ordinary post-treatments such as extraction, concentration, and filtration are performed, and if necessary, purification can be appropriately performed by known means such as recrystallization and various types of chromatography.

As the compound (I-3), for example, Table 2
Compounds (I-3) [compounds (I-) comprising the types of the respective substituents corresponding to the compounds 3, 9, 15 and the like shown in
3) ₃ , (I-3) ₉ , (I-3) _15, 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, Z is a sulfur atom, and n is 8. ].

(Synthesis Method 4) In the synthesis of compound (I-4) [compound in which R ¹ in compound (I) is a fluorine atom], compound (I-3) and a fluorinating agent are usually dissolved in a solvent or The reaction can be performed in the absence of a solvent.

[0063]

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(In the formula, R ² , Z and n have the same meanings as described above.) As the solvent, the chlorinated or non-chlorinated aromatic, aliphatic or alicyclic compound described in Synthesis Method 1 is used. Hydrocarbons, ethers, and mixtures of the above solvents.

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 (-3) is in the range of 5 to 80% by weight.
It is preferred that the concentration of 3) is 10 to 70% by weight. Examples of the fluorinating agent include fluorinated alkylaminosulfurs.

[0066]

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For example, diethylaminosulfur trifluoride (DAST) or the like can be used. The compound can be used in an amount of 1 to 5 moles based on the compound (I-3), but preferably 1 to 5 times.
It is preferably twice as much as the molar amount.

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, 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) In addition to Synthesis Method 4, compound (I-4) [compound (I) wherein R ¹ is a fluorine atom] Can be carried out in a solvent or in the absence of a solvent.

[0070]

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(In the formula, R ² , R ⁴ , Z, n and M have the same meanings as described above.) As the solvent, N, N-dimethylformamide, N, N
Amides such as -dimethylacetamide; 1,3-dimethyl-2-imidazoline; dimethylsulfoxide; sulfolane;

The amount of the solvent used depends on the amount of the compound (I
The compound (I-) can be used in such a manner that the concentration of -1) is in the range of 5 to 80% by weight.
It is preferred that the concentration of 1) is 10 to 70% by weight. Examples of the fluorine compound include an alkali metal fluorine compound represented by the following formula: MF (IV) (wherein M has the same meaning as described above),
Preferably, cesium fluoride, potassium fluoride and the like are used.

The amount of the compound (I-1)
Can be used at 1 to 5 moles, preferably 1.2 to 3 moles to the compound (I-1). The reaction temperature is not particularly limited, but is in a temperature range from room temperature to the boiling point of the solvent used or lower, 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. Target compound (I-4) produced by Synthetic methods 4 and 5
After completion of the reaction, can be subjected to ordinary post-treatments such as extraction, concentration, and filtration, and can be appropriately purified by a known means such as recrystallization or various types of chromatography, if necessary.

As the compound (I-4), for example, the compounds shown in Table 2
Compounds 4, 10, 12, 16, 18, and 2 shown in
Each compound (I) consisting of each substituent type corresponding to
-4) [Compound (I-4) ₄ , (I-4) ₁₀ , (I-
4) ₁₂ , (I-4) ₁₈ , (I-4) _20, etc. For example, the compound (I-4) ₄ is the compound (I)
In the formula, R ¹ is a fluorine atom, R ² is a methyl group, Z is a sulfur atom, and n is 8. ].

Examples of the pests which can be controlled with the compound (I) of the present invention include agricultural and horticultural pests [eg, Hemiptera (Cyberidae, leafhoppers, aphids, whiteflies, etc.), and Lepidoptera (Coleoptera) , 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 adjuvant, etc. are blended by a conventional method (eg, powder, emulsion, fine granule, granule, wettable powder, 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, 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 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.

[0081]

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)] Synthesis of 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, the N, N-dimethylformamide layer was separated, 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. 192-194 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm 1.66-1.82 (dd, 3H), 5.85-6.
21 (dq, 1H), 8.83 (s, 1H)

(4) 6- (1-acetoxyethyl)-
Synthesis of 4,5-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. Then, the solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 5: 1) to give the target compound as a pale yellow liquid. 2.8 g were obtained.

(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).

[0091]

[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-
Synthesis of (8-methylthiooctylamino) pyrimidine (compound 1) 8-methylthiooctylamine (2.5 g) and triethylamine (2.0 g) were dissolved in toluene (20 ml), and 6- (1-chloroethyl) -4 , 5-Dichloropyrimidine (3.0 g) was added, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, the target compound 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 purified by column chromatography (Wakogel C-200, eluted with toluene) to give 2.4 g of the desired compound as a pale yellow oil.

(2) 6- (1-acetoxyethyl) -5
Synthesis of -chloro-4- (8-methylthiooctylamino) pyrimidine (compound 2) 5-chloro-6- (1-chloroethyl) -4- (n-decylamino) pyrimidine (1.2 g) was added to DMF (20 m
1), then potassium acetate (0.5 g) and potassium carbonate (0.5 g) were added, and the mixture was stirred at 60 ° C. for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, water was added, 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 subjected to column chromatography (Wakogel C-200, toluene: ethyl acetate =
(10: 1 elution) to give 1.4 g of the target compound as a pale yellow oily liquid.

(3) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- (8-methylthiooctylamino) pyrimidine (compound 3) 6- (1-acetoxyethyl) -5-chloro-4- (8
-Methylthiooctylamino) pyrimidine (1.2 g)
Was dissolved in an ethanol solution (a 1: 1 mixture of ethanol and a 10% aqueous sodium hydroxide solution, 20 ml), and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, ethanol was distilled off under reduced pressure, 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 purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 5: 1) to obtain 1.2 g of the target compound as a pale yellow oil.

(4) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- (8-methylthiooctylamino) pyrimidine (compound 4) 5-chloro-6- (1-hydroxyethyl) -4- (8
-Methylthiooctylamino) pyrimidine (0.6 g)
Was dissolved in dichloromethane (30 ml), diethylaminosulfur trifluoride (0.6 g) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hour. After the reaction is completed, add ice water (3
0 ml), and the target compound 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 obtained oil was purified by column chromatography (Wakogel C-200, toluene: ethyl acetate = 20: 1 elution) to obtain 0.3 g of the target compound as a colorless oil.

(5) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- [6- (n-propylthio) -hexylamino] pyrimidine (compound 10) 5-chloro-6- (1-chloroethyl) ) -4- (6-
(N-Propylthio) -hexylamino) pyrimidine (3.5 g) was converted to N, N-dimethylformamide (30 m).
l), cesium fluoride (3.0 g) was added, and the mixture was heated to 120 to 140 ° C and stirred for 12 hours. After completion of the reaction, water (50 ml) was 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 resulting oil was subjected to column chromatography (Wakogel C-20).
0, toluene: ethyl acetate = 9: 1) to give 2.0 g of the target compound as a pale yellow oily liquid.
Obtained.

(6) 6- (1-acetoxyethyl) -5
Synthesis of -chloro-4- [6- (n-propylthio) -hexylamino] pyrimidine (compound 6) 6- (1-acetoxyethyl) -4,5-dichloropyrimidine (2.35 g) and triethylamine (1.2 g) )
Was dissolved in toluene (30 ml), and then 6-n-
Propylhexylamine (1.75 g) was added, and the mixture was heated under reflux for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 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 resulting oil was subjected to column chromatography (Wakogel C-200, toluene: ethyl acetate = 9:
Purification by 1 elution) yielded 3.0 g of the target compound as a pale yellow oily liquid.

(7) Synthesis of other target compounds (I) in Tables 2 to 4 According to the methods described in the above (1) to (6), other target compounds (I) in Tables 2 to 4 Was synthesized. The compounds synthesized as described above are shown in Tables 2 to 4.

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

[Table 4]

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 (product) 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 against Conaga Compounds (I) prepared according to Example 2 and shown in Tables 2 to 4
Each hydration agent in water containing a surfactant (0.01%).
It 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 5 shows the results.

[0107]

[Table 5]

(2) Efficacy test against brown planthopper Compound (I) shown in Tables 2 to 4 prepared according to Example 2
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 are shown in Table 6 using the four-step evaluation method described in the above (1).

[0109]

[Table 6]

(3) Efficacy test on adult female spider mite, Tetranychus urticae Compound (I) prepared according to Example 2 and shown in Tables 2 to 4
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 7 shows the results.

[0111]

[Table 7]

(4) Efficacy test on sweet potato nematodes Compound (I) shown in Tables 2 to 4 prepared according to Example 2
Was diluted to 20 ppm with water, and 0.5 ml of each was added to a test tube. Further, an aqueous solution containing 30 to 40 sweet potato nematodes in these was added to 0.5 m of each.
One by one. Next, it was left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects was counted under a microscope (40-fold visual field) to determine the nematicidal rate. The evaluation of the nematicidal effect was performed in four stages (A: 100 to 90%, depending on the range of the nematicidal rate).
B: 89 to 80%, C: 79 to 60%, D: 59% or less). Table 8 shows the results.

[0113]

[Table 8]

(5) Test for controlling efficacy against barley powdery mildew (preventive effect) 10 barleys (cultivar: black wheat) were grown per pot in plastic flowerpots having a diameter of 6 cm, and seedlings at the 1.5 leaf stage In addition, each wettable powder of the compound (I) shown in Tables 2 to 4 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%). The chemical was sprayed at a rate of 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.

[0115]

[Table 9]

(6) Test for controlling efficacy against wheat leaf rust (preventive effect) Wheat (cultivar: Kobushi wheat) was grown 10 per pot in a plastic flower pot having a diameter of 6 cm. A wettable powder of compound (I) shown in Tables 2 to 4 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 uniformly sprayed and inoculated 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 are shown in Table 10 by the six-step evaluation method described in the above (5).

[0117]

[Table 10]

[0118]

Industrial Applicability The novel alkylaminopyrimidine derivative of the present invention has an excellent pest control effect against insecticide, miticide, sterilization and the like.

Claims (3)

(57) [Claims] (1) The following formula: (Wherein, R ¹ represents a halogen atom, a hydroxyl group, or a lower acyloxy group; R ² represents an alkyl group having 1 to 12 carbon atoms; Z represents an oxygen atom or a sulfur atom;
Represents an integer. ) An alkylaminopyrimidine derivative represented by the formula: 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 , Z and n have the same meanings as in claim 1), and are reacted with an alkylamine represented by the formula (I). A method for producing an aminopyrimidine derivative. 3. A pesticidal composition comprising an alkylaminopyrimidine derivative represented by the formula (I) according to claim 1 as an active ingredient.