JP2673848B2 - 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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(In the formula, R ¹ is a halogen atom, a hydroxyl group,
Represents a lower acyloxy group, a lower alkoxy group or a lower alkylthio group; R ² represents a hydrogen atom, a lower alkyl group or a lower cycloalkyl group; R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )). Second
The invention of is represented by 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 and R ³ have the same meanings as described above), and an alkylamine pyrimidine of the above-mentioned formula (I) characterized by reacting with an alkylamine. The present invention relates to a method for producing a derivative.
A third invention provides the following formula (I-1):

[0011]

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(In the formula, R ² and R ³ have the same meanings as described above. R ⁴ represents a halogen atom.) And a pyrimidine derivative represented by the following formula (IV):

[0013]

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In the above formula (I), R ¹ is a lower acyloxy group, which is characterized by reacting with a lower aliphatic carboxylic acid represented by the formula (wherein R ⁵ represents a lower acyloxy group). The present invention relates to a method for producing an alkylaminopyrimidine derivative. A fourth invention is the following formula (I-2):

[0015]

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

[0017]

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(In the formula, M represents an alkali metal.) An alkylaminopyrimidine derivative represented by the formula (I) described above, wherein R ¹ is a hydroxyl group, is reacted with an inorganic base represented by the formula: It relates to the manufacturing method.
A fifth invention is the following formula (I-3):

[0019]

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In the above formula (I), the alkylaminopyrimidine derivative represented by the formula (wherein R ² and R ³ are as defined above) is reacted with a fluorinating agent. The present invention relates to a method for producing an alkylaminopyrimidine derivative in which R ¹ is a fluorine atom.
A sixth invention is an alkylaminopyrimidine derivative represented by the above formula (I-1) and the following formula (VI):

[0021]

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(In the formula, M has the same meaning as described above.)
The present invention relates to a process for producing an alkylaminopyrimidine derivative represented by the above formula (I), wherein R ¹ is a fluorine atom, which is characterized by reacting with a fluorine compound represented by A seventh invention relates to an alkylaminopyrimidine derivative represented by the above formula (I-1) and the following formula (VI
I):

[0023]

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(In the formula, R ⁶ represents a lower alkyl group; Y
Represents an oxygen atom or a sulfur atom. The present invention relates to a process for producing an alkylaminopyrimidine derivative in which R ¹ is a lower alkoxy group or a lower alkylthio group in the above formula (I), which is characterized by reacting with a compound represented by the formula (1). An eighth invention relates to a pest control agent containing as an active ingredient the alkylaminopyrimidine derivative represented by the above formula (I).

Hereinafter, the present invention will be described in detail. A novel alkylaminopyrimidine derivative (I) which is the above-mentioned target compound [compounds (I-1), (I-2), (1-
3), (I-4) and (1-5)], and R ¹ in the compounds (II) to (VIII) which are raw materials for producing the same.
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, Y and M are as follows.

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

In R ¹ , the halogen atom (eg, chlorine atom, iodine atom, bromine atom, fluorine atom, etc.) is preferably chlorine atom or fluorine atom; and the lower acyloxy group has carbon atom number. 1-4
Linear or branched (for example, acetyloxy group, n-propionyloxy group, i-propionyloxy group, n-butyroyloxy group, i-butyroyloxy group, t-butyroyloxy group, etc.), preferably acetyloxy group The lower alkoxy group is a linear or branched one having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i- Butoxy group, t-butoxy group, etc.), preferably methoxy group; the lower alkylthio group is a linear or branched one having 1 to 4 carbon atoms (eg, methylthio group, ethylthio group, n-propylthio group). Group, i-propylthio group, n-butylthio group,
i-butylthio group, t-butylthio group, etc.), preferably methylthio group, ethylthio group.

Examples of R ² include a hydrogen atom, a lower alkyl group and a lower cycloalkyl group.

The lower alkyl group for R ² is linear or branched having 1 to 4 carbon atoms (eg, methyl group, ethyl group, n-propyl group, i-
Propyl group, n-butyl group, i-butyl group, t-butyl group, etc.), preferably methyl group, ethyl group; lower cycloalkyl group preferably has 3 to 10 carbon atoms.
6 cycloalkyl groups (eg cyclopropyl group, 2
-Or a 3-methylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc. is preferable, and a cyclopropyl group is more preferable.

R ³ is a hydrogen atom or a carbon atom number 1 to
Examples thereof include an alkyl group having 20 atoms; preferably a linear or branched one having 1 to 18 carbon atoms (for example, in addition to the lower alkyl group described above as R ² , pentyl group, hexyl group). Group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
A tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, etc. are preferable, and a linear or branched one having 1 to 11 carbon atoms is more preferable.

R ⁴ and X are halogen atoms (for example, R 4
¹ as described above).

M represents an alkali metal.

R ⁵ represents a lower acyloxyl group (lower aliphatic carboxylic acid residue) corresponding to R ¹ .

[0034] In ^{R 6} -Y, ^R 6 represents a lower alkyl group corresponding to ^{R 1;} Y in ^{R 1}

Represents the corresponding oxygen atom and sulfur atom. That is, R ⁶ -Y represents a lower alkoxy group or a lower alkylthio group corresponding to R ¹ . The compound (I) of the present invention can be synthesized by the following synthetic methods 1 to 6. (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.

[0036]

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(In the formula, R ¹ , R ² , R ³ 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, and for example, benzene, Chlorinated or unchlorinated aromatics such as 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 and the like;
Ketones such as acetone and methyl ethyl ketone;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, etc .; Nitriles such as acetonitrile, propionitrile, etc .; Organic bases such as triethylamine, pyridine, N, N-dimethylaniline, etc .; 1 , 3-dimethyl-2-imidazolidinone;
Dimethyl sulfoxide; a mixture of the above solvents and the like can be mentioned.

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 and includes, for example,
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 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 is usually 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) used in the present invention is usually the starting compound (VII) and compound (V) as shown below.
And III) in a solvent.

[0043]

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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 used is such that the concentration of the compound (VII) is 5 to 8.
It can be used in a concentration range of 0% 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 raw material compound used is the amount of the 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 easily manufactured by carrying out as shown in the following formula.

[0046]

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(Wherein X has the same meaning as described above; R
Represents a hydrogen atom, a hydroxyl group or a halogen atom. ) The desired compound (II) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration after completion of the reaction, and if necessary, known means such as recrystallization and various chromatographies. Can be appropriately purified.

Examples of the compound (II) include the starting compounds (II-1), (II-2), and
(II-3) etc. can be mentioned.

The compound (III) used in the present invention can be prepared according to, for example, J. Am. Chem. Soc. , 66 volumes, 1516
According to the method described on page (1744), etc., it can be produced by carrying out as shown in the following formula.

[0050]

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(In the formula, R ² and R ³ have the same meanings as described above.) As the compound (III), for example, Table 2
Each compound (III) [compound (III) ₁ to ₁ consisting of the type of each substituent corresponding to compounds 1 to 68 shown in 10
(III) ₆₈ . For example, this compound (II
I) ₁ is R ^{2 in the} formula represented by the compound (III)
Means a hydrogen atom and R ³ is an ethyl group. ]
Can be mentioned.

Examples of the compound (I) are shown in Tables 2-1.
Compounds 1 to 68 shown in 0 [Compound 1 means that R ^{1 in the} formula of Compound (I) is a chlorine atom, R ² is a hydrogen atom, and R ³ is an ethyl group. ].

(Synthesis Method 2) Compound (I-2) [compound (I) in which R ¹ is a lower acyloxyl group] is usually synthesized 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.

[0054]

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(In the formula, R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.) Examples of the solvent include acetic acid and proropionic acid in addition to the solvent described in Synthesis Method 1. Examples thereof include aliphatic carboxylic acids, mixtures thereof, and the like; N, N-dimethylformamide and the same aliphatic carboxylic acid as the acyloxyl group to be introduced are preferable.

The amount of the solvent used is 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 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 1 to 50 hours. As the compound (IV), a commercially available product can be used.

The desired compound (I-2) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration after the reaction is completed, and if necessary, recrystallization, various chromatographies, etc. It can be appropriately purified by a known method.

Examples of the compound (I-2) are shown in Table 2
Compounds 2, 6, 18, 51, 53, 5 shown in 10
5,57,59,61,63,65, etc., each compound (I-2) consisting of the type of each substituent [Compound (I-
2) ₂ , (I-2) ₆ , (I-2) ₁₈ , (I-2)
₅₁ , (I-2) ₅₃ , (I-2) ₅₅ , (I-2)
₅₇ , (I-2) ₅₉ , (I-2) ₆₁ , (I-2)
₆₃ , (I-2) _{65 and the} like. For example, the compound (I-2) ₂ means that R ^{1 in the} formula represented by the compound (I) is an acetyloxy group, R ² is a hydrogen atom, and R ³ is an ethyl group. ].

(Synthesis Method 3) The compound (I-3) [compound (I) wherein R ¹ is a hydroxyl group] is synthesized as follows:
Usually, compound (I-2) and compound (V) in the presence of a base
And a reaction in a solvent.

[0062]

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(In the formula, R ² , R ³ , R ⁵ 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 can be used. Mention may be made of mixtures (eg methanol, ethanol, propanol, butanol, etc.), water and mixtures of said solvents; preferably mixtures of alcohols and water. The amount of the solvent used is the compound (I-
It can be used so that the concentration of 2) falls within the concentration range of 5 to 80% by weight, but it is preferable to use the compound (I-
It is preferable to use it so that the concentration of 2) is 10 to 70% 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 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 desired compound (I-3) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration after the completion of the reaction, and if necessary, recrystallization, various chromatography and the like. It can be appropriately purified by a known method.

Examples of the compound (I-3) are shown in Table 2
Compounds 3, 7, 19, 52, 54, 5 shown in 10 to 10
6,58,60,62,64,66 etc. and each compound (I-3) [compound (I-
3) ₃ , (I-3) ₇ , (I-3) ₁₉ , (I-3)
₅₂ , (I-3) ₅₄ , (I-3) ₅₆ , (I-3)
₅₈ , (I-3) ₆₀ , (I-3) ₆₂ , (I-3)
₆₄ , (I-3) _66, etc. For example, the compound (I-3) ₃ means that in the formula represented by the compound (I), R ¹ is a hydroxyl group, R ² is a hydrogen atom, and R ³ is an ethyl group. ].

(Synthesis Method 4) Compound (I-4) [compound (I) in which R ¹ is a fluorine atom] is usually synthesized by mixing compound (I-3) with a fluorinating agent in a solvent. It can be carried out by reacting in the absence of solvent.

[0070]

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

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 (-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. As the fluorinating agent, the following formulas;

[0073]

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Diethylaminosulfur trifluoride (DAST) or the like represented by 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 within the temperature range from the ice-cooling temperature to the boiling point of the solvent used or less, preferably 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) The compound (I-4) was synthesized by
In addition to the synthesis method 4, it can be carried out by reacting the compound (I-1) with a fluorine compound in a solvent or without solvent.

[0077]

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(In the formula, R ² , R ³ , R ⁴ and M have the same meanings as described above.) As the solvent, amides such as N, N-dimethylformamide and N, N-dimethylacetamide; 1,3-dimethyl-2-imidazoline; dimethyl sulfoxide; sulfolane; a mixture of the above solvents, and the like.

The amount of the solvent used is 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. The fluorine compound has the following formula;

[0080]

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(In the formula, M has the same meaning as described above.)
Alkaline earth metal fluorine compounds represented by the following are mentioned; preferably cesium fluoride, potassium fluoride and the like are preferable.

The amount of the compound used is 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 it is within the temperature range from room temperature to the boiling point of the solvent to be used, 100
~ 140 ° C is preferred. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 1 to 8 hours.

The target compound (I-4) produced by the synthetic methods 4 and 5 is subjected to usual post-treatments such as extraction, concentration and filtration after the completion of the reaction, and if necessary, recrystallization and various chromatographies. It can be appropriately purified by a known means such as.

Examples of the compound (I-4) are shown in Table 2
Compounds 4,8,10,12,14,1 shown in
6, 20, 22, 24, 26, 28, 30, 32, 3
4,36,38,40,42,44,46,68 etc. each compound (I-4) consisting of the kind of each substituent
[Compound (I-4) ₄ , (I-4) ₈ , (I-
4) ₁₀ , (I-4) ₁₂ , (I-4) ₁₄ , (I-
4) ₁₆ , (I-4) ₂₀ , (I-4) ₂₂ , (I-
4) ₂₄ , (I-4) ₂₆ , (I-4) ₂₈ , (I-
4) ₃₀ , (I-4) ₃₂ , (I-4) ₃₄ , (I-
4) ₃₆ , (I-4) ₃₈ , (I-4) ₄₀ , (I-
4) ₄₂ , (I-4) ₄₄ , (I-4) ₄₆ , (I-
4) _{Called 68} etc. For example, this compound (I-4)
₄ means that R ^{1 in the} formula (I) is a fluorine atom, R ² is a hydrogen atom, and R ³ is an ethyl group. ].

(Synthesis Method 6) Compound (I-5) [compound (I) in which R ¹ is a lower alkoxy group or a lower alkylthio group] is usually synthesized by compound (I-
The reaction can be carried out by reacting 1) with compound (VII) in a solvent or in the absence of a solvent, but it is preferable to react in the presence of a base in order to accelerate the reaction.

[0087]

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(In the formula, R ² , R ³ , R ⁴ , R ⁶ and Y have the same meanings as described above.) Examples of the solvent include the solvents described in Synthesis Method 1. The amount of the solvent used can be such that the concentration of the compound (I-1) is in the concentration range of 5 to 80% by weight, but the concentration of the compound (I-1) is preferably 10. It is advisable to use it in an amount of up to 70% by weight.

Examples of the base include the bases described in Synthesis Method 1, but inorganic bases are preferable. The amount of the base used can be 1 to 5 times the molar amount of the compound (I-1), but is preferably 1
It is preferably ˜3 times the molar amount.

The reaction temperature is not particularly limited, but it is within the temperature range from room temperature to the boiling point of the solvent to be used, or from room temperature to
60 ° C. is preferred. 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 compound (VII) used is
The amount of compound (VII) is 1 to 5 times, and preferably 1 to 2 times the mol of -1). Compound (V
As II), commercially available products can be used.

The desired compound (I-5) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration after the completion of the reaction, and if necessary, recrystallization, various chromatography, etc. It can be appropriately purified by a known method.

Examples of the compound (I-5) are shown in Table 7
And each compound (I-5) consisting of the kind of each substituent corresponding to the compounds 47 to 50 shown in 8 and 8 [Compound (I-
5) ₄₇ , (I-5) ₄₈ , (I-5) ₄₉ , (I-
5) _{Referred to} as ₅₀ . For example, this compound (I-5)
₄₇ means that R ^{1 in the} formula (I) is a methoxy group, R ² is a hydrogen atom, and R ³ is an ethyl group. ].

The pests which can be controlled by the compound (I) of the present invention include agricultural and horticultural pests [eg, Hemiptera (Plants, leafhoppers, aphids, whiteflies, etc.), Lepidoptera (Beetle beetles). , Plutella xylostella, Pseudococcidae, Beetle moth, Singing beetle, Pieris rapae, Coleoptera (Galloridae, Weevil, Chrysomelidae, Scarabaeidae, etc.) )], Sanitary pests (for example, flies, mosquitoes, cockroaches, etc.), stored-grain pests (Beetle beetles, bean weevils, etc.), root-knot nematodes, pine wood nematodes, and ticks, and agro-horticultural pathogens ( For example, wheat leaf rust, barley powdery mildew, cucumber beet disease, rice blast disease, corn Epidemics, etc.) can be mentioned.

The pest control agent of the present invention is effective for controlling insecticide
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).

As the carrier, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbonization 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, dimethylsulfoxide, etc.), water; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection), and the like.

Examples of surfactants and dispersants that can be used to improve the performance of the agent such as adhesion to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading and the like include, for example, alcohol sulfates and alkyls. Examples thereof include sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like. 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 production of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in suitable combination according to the purpose.
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 sprayed on the plant foliage, soil, water surface of paddy fields or directly applied for various purposes according to the purpose.

[0100]

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 raw material compound (II)] (1) Synthesis of 6- (1-chloroethyl) -4,5-dichloropyrimidine (raw material 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) Other starting compounds (I
Synthesis of I) The starting compound (II) was synthesized in the same manner as in (1) above.

[0102]

[Table 1]

Example 1 [Synthesis of Compound (I)] The target compound (I) was synthesized using the starting compound (II) obtained in Reference Example 1. (1) 6- (1-chloroethyl) -5-chloro-4-
Synthesis of (n-decylamino) pyrimidine (Compound 17) n-decylamine (8.2 g) and triethylamine (1
5.1 g) and toluene (50 ml) were dissolved, and 6-
(1-Chloroethyl) -4,5-dichloropyrimidine (10.4 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 oily substance was purified by column chromatography (Wakogel C-200, eluted with toluene) to obtain 10.5 g of a target compound as a pale yellow oily liquid.

(2) 6- (1-acetoxyethyl) -5
Synthesis of -chloro-4- (n-decylamino) pyrimidine (Compound 18) 5-chloro-6- (1-chloroethyl) -4- (n-decylamino) pyrimidine (10.1 g) was added to acetic acid (100 g).
ml), then potassium acetate (19.7 g)
And potassium carbonate (4.1 g) were added, and the mixture was heated under reflux for 30 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 =
Purification (10: 1 elution) gave 5.6 g of the desired compound as a pale yellow oily liquid.

(3) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- (n-decylamino) pyrimidine (Compound 19) 6-Ethoxy- (1-acetoxyethyl) -5-chloro-4- (N-Decylamino) pyrimidine (5.1 g) was dissolved in an ethanol solution (1: 1 mixture of ethanol and 10% aqueous sodium hydroxide solution, 100 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 oily substance was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 5: 1) to obtain 3.8 g of the target compound as colorless prism crystals.

(4) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- (n-decylamino) pyrimidine (Compound 20) 5-chloro-6- (1-hydroxyethyl) -4- (n
-Decylamino) pyrimidine (2.5 g) was dissolved in dichloromethane (30 ml), diethylaminosulfur trifluoride (2.2 g) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hr. After the reaction was completed, ice water (30 ml) was added, 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, eluted with toluene: ethyl acetate = 20: 1) to obtain 1.9 g of the target compound as a colorless oily liquid.

(5) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- (n-hexylamino) pyrimidine (Compound 10) 5-chloro-6- (1-chloroethyl) -4- (n -Hexylamino) pyrimidine (2.7 g) was dissolved in N, N-dimethylformamide (25 ml), cesium fluoride (1.8 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 obtained oily substance was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 1: 9) to obtain 1.4 g of the target compound as a pale yellow oily liquid.

(6) Synthesis of 5-chloro-6- (1-methoxyethyl) -4- (n-heptylamino) pyrimidine (Compound 48) 5-chloro-6- (1-chloroethyl) -4- (n -Heptylamino) pyrimidine (2.90 g) was added to methanol (10 ml) and N, N-dimethylformamide (10 m).
It was dissolved in a mixed solution with l), and then sodium methoxide 28% methanol solution (1.0 g) was added, followed by stirring at 60 ° C. for 6 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 oily substance was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 8: 2) to obtain 1.80 g of the target compound as colorless crystals.

(7) Synthesis of 5-chloro-6- (1-methylthioethyl) -4- (n-pentylamino) pyrimidine (Compound 49) 5-chloro-6- (1-chloroethyl) -4- (n -Pentylamino) pyrimidine (2.90 g) was dissolved in methanol (30 ml), 15% aqueous solution of methanethiol sodium salt (5.0 g) was added, and the mixture was stirred at room temperature for 3 hr. 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 oily substance was purified by column chromatography (Wakogel C-200, eluted with toluene) to obtain 1.8 of the target compound as a colorless oily liquid.
g was obtained.

(8) Synthesis of Other Target Compound (I) Other target compound (I) was synthesized according to the method described in (1) to (7) above. The compounds synthesized as described above are shown in Tables 2 to 10.

[0112]

[Table 2]

[0113]

[Table 3]

[0114]

[Table 4]

[0115]

[Table 5]

[0116]

[Table 6]

[0117]

[Table 7]

[0118]

[Table 8]

[0119]

[Table 9]

[0120]

[Table 10]

Example 2 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound 2, 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 lignin sulfonate were uniformly mixed, and then a small amount of water was added and kneaded, and then granulated and dried to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 2, 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 (commercial product) Name; made by Kao Co., Ltd.) and 0.5 parts by weight, and
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of emulsion To 20 parts by weight of compound 2 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Kasei Co., Ltd.) were added and uniformly mixed and dissolved to obtain an emulsion. .

(4) Preparation of Dust Preparation 5 parts by weight of compound 2, 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 diamondback moth A moisturizer of each compound (I) shown in Tables 1 to 10 prepared according to Example 2 was treated with a surfactant (0.01%). Was diluted to 300 ppm with water containing cabbage, cabbage leaf pieces (5 × 5 cm) were dipped in each of these chemical solutions for 30 seconds, placed in each plastic cup one by one, and air dried. Next, 10 moths (3rd instar larvae) were released into each of these cups, covered, and allowed to stand in a constant temperature room at 25 ° C. After 2 days, the number of live and dead insects in each cup was counted to determine the mortality. I asked. The insecticidal effect is evaluated in four stages (A: 100%, B: 99-) depending on the range of mortality.
80%, C: 79-60%, D: 59% or less). Table 11 shows the results.

[0126]

[Table 11]

(2) Efficacy test against brown planthopper Each wettable powder of compound (I) shown in Tables 2 to 10 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%). Then, rice seedlings were immersed in each of these chemical solutions for 30 seconds, air-dried, and then inserted into each glass cylinder. Next, 10 glass larvae of the 4th instar planthopper were released into each of these glass cylinders, covered with a porous cover, and allowed to stand in a constant temperature room at 25 ° C., and after 4 days, the number of live and dead insects in each glass cylinder was counted and killed. I asked for the rate. The results of the insecticidal effect evaluation are shown in Table 12 by the four-step evaluation method described in (1) above.

[0128]

[Table 12]

(3) Efficacy test against female adult worms of the genus Nami, each wettable powder of the compound (I) shown in Tables 2 to 10 prepared according to Example 2 was added with water containing a surfactant (0.01%) to obtain 300 ppm. Each kidney bean leaf piece (diameter: 2)
0 mm) was immersed for 15 seconds each. 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 result of the evaluation of the acaricidal effect is four levels (A: 10) depending on the range of the acaricidal rate.
0%, B: 99-80%, C: 79-60%, D: 59
% Or less). Table 13 shows the results.

[0130]

[Table 13]

(4) Control Efficacy Test for Barley Powdery Mildew (Preventive Effect) 10 barleys (cultivar: black wheat) were grown in a plastic flower pot with a diameter of 6 cm, and 1.5 leaf stage seedlings were grown. In addition, each wettable powder of the compound (I) shown in Tables 2 to 10 prepared according to Example 2 was treated with a surfactant (0.01%).
Each of them was sprayed with 20 ml per one pot by diluting each to 500 ppm with water containing water. 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 14 shows these results.
Shown in

[0132]

[Table 14]

(5) Control Efficacy Test for Wheat Leaf Rust (Preventive Effect) Ten wheat (cultivar: Kobushi Wheat) was grown in a plastic flower pot having a diameter of 6 cm, and 10 seeds were cultivated at 1.5 leaf stage. A wettable powder of the compound (I) shown in Tables 2 to 10 prepared according to Example 2 was treated with 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 15 by the 6-step evaluation method described in (4) above.

[0134]

[Table 15]

[0135]

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

Claims (8)

(57) [Claims] (1) The following formula: (In the formula, R ¹ represents a halogen atom, a hydroxyl group, a lower acyloxy group, a lower alkoxy group or a lower alkylthio group; R ² represents a hydrogen atom, a lower alkyl group or a lower cycloalkyl group; R ³ represents a hydrogen atom or 1 to 2 carbon atoms
Represents an alkyl group of 0. ) 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: (In the formula, R ² and R ³ have the same meanings as described in claim 1.) An alkylamino represented by the formula (I) according to claim 1, which is characterized by reacting with an alkylamine. Process for producing pyrimidine derivative. 3. The following formula: (In the formula, R ² and R ³ have the same meanings as described in claim 1;
R ⁴ represents a halogen atom. ) And an alkylaminopyrimidine derivative represented by the following formula: (Wherein R ⁵ represents a lower acyloxy group) is reacted with a lower aliphatic carboxylic acid, and in the formula (I) according to claim 1, R ¹ represents a lower acyloxy group. Process for producing alkylaminopyrimidine derivative. 4. The following formula: (In the formula, R ² and R ³ are as defined in claim 1;
R ⁵ represents a lower acyloxy group. ) And an alkylaminopyrimidine derivative represented by the following formula: The method for producing an alkylaminopyrimidine derivative represented by the formula (I) according to claim 1, wherein R ¹ is a hydroxyl group, characterized by reacting with an inorganic base represented by the formula (wherein M represents an alkali metal). . 5. The following formula: (In the formula, R ² and R ³ have the same meanings as described in claim 1.) An alkylaminopyrimidine derivative represented by the formula (1) and a fluorinating agent are reacted with each other, and the formula (I) according to claim 1. ^1. A process for producing an alkylaminopyrimidine derivative, wherein R ¹ is a fluorine atom. 6. An alkylaminopyrimidine derivative represented by the formula (I-1) according to claim 3 and the following formula: (In the formula, M has the same meaning as described in claim 4.) An alkyl represented by formula (I) in which R ¹ is a fluorine atom is reacted with a fluorine compound represented by formula (4). Process for producing aminopyrimidine derivative. 7. An alkylaminopyrimidine derivative represented by the formula (I-1) according to claim 3 and the following formula: (Wherein, R ⁶ represents a lower alkyl group; Y represents an oxygen atom or a sulfur atom.) R ¹ in the formula (I) according to claim 1 which comprises reacting a compound represented by
A process for producing an alkylaminopyrimidine derivative, wherein is a lower alkoxy group or a lower alkylthio group. 8. A pest control agent comprising the alkylaminopyrimidine derivative represented by the formula (I) according to claim 1 as an active ingredient.