JPH05201999A - Aralkylaminopyrimidine derivative, its production and pest control agent - Google Patents

Abstract

PURPOSE:To obtain the subject new compound useful for pest control agents such as insecticides, acaricides, nematicides and fungicides, etc., by reacting a specific halogenated pyrimidine derivative with an aralkylamine compound. CONSTITUTION:A pyrimidine derivative of formula I (R<1> is halogen, lower acyoxy, hydroxy, lower alkoxy, lower alkylthio; X is halogen) [e.g. 6-(1- chloroethyl)-4,5-dichloropyrimidine] is reacted with an aralkylamine of formula II (R<2> is lower alkyl, H, cycloalkyl; R<3> is lower haloalkoxy, H, lower alkyl, lower alkoxy, halogen, etc.; n is 1-5) [e.g. 1-(4-difluoromethoxyphenyl)ethylamine] in the presence of a triethylamine in a solvent such as toluene for 5hr under refluxing to obtain an aralkylaminopyrimidine derivative of formula III.

Description

Detailed Description of the Invention

[0001]

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

[0002]

Description of the Prior Art Since the aralkylaminopyrimidine derivative of the present invention is a novel compound, it is not known to have its pest controlling activity.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a novel aralkylaminopyrimidine derivative, a process for producing the same, and pests useful as insecticides, acaricides, nematicides, fungicides containing the same as active ingredients. It is to provide a control agent.

[0004]

Means for Solving the Problems As a result of investigations for solving the above problems, the present inventors have found that a novel aralkylaminopyrimidine derivative is useful as an insecticide, acaricide, nematicide, fungicide, etc. As a result, they have found that they have remarkable control activity as a pest control agent, and have completed the present invention. That is, the present invention is as follows. The first invention is represented by the following formula (I):

[0005]

[Chemical 4]

(Wherein R ¹ represents a halogen atom, a lower acyloxy group, a hydroxyl group, a lower alkoxy group or a lower alkylthio group; R ² represents a lower alkyl group, a hydrogen atom or a cycloalkyl group; R ³ represents a lower halo An alkoxy group,
Represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower alkylthio group, a nitro group, a lower haloalkyl group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower haloalkylthio group or a hydroxyl group; n is 1 to 5 Represents an integer. ) Related to aralkylaminopyrimidine derivatives. In the compound (I) of the present invention, the carbon atom marked with * is an asymmetric carbon atom, and each of the individual optical isomers, racemates, diastereomeric compounds or mixtures thereof are included in the present invention. .. The second invention is the following formula (II):

[0007]

[Chemical 5]

(In the formula, R ¹ has the same meaning as described above;
X represents a halogen atom. ) And the following formula (III):

[0009]

[Chemical 6]

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

The third invention relates to a pest control agent containing the aralkylaminopyrimidine derivative represented by the above formula (I) as an active ingredient.

The present invention will be described in detail below. A novel aralkylaminopyrimidine derivative (I) which is the above-mentioned target compound [compounds (I-1), (I-2), (I-3), (I-
4) and (I-5)], the compound (I
R ¹ in I) ~ (VIII), R 2, R 3, R 4,
R ⁵ , R ⁶ , X, Y, M and n are as follows.

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

Examples of the halogen atom for R ¹ include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably a chlorine atom, a fluorine atom and a bromine atom.

Examples of the lower acyloxy group for R ¹ include those having a linear or branched alkyl group having 2 to 6 total carbon atoms; preferably, the total number of carbon atoms is 2 to 4 groups are preferable (for example, acetyloxy group, propionyloxy group, n-butyroyloxy group, i-butyroyloxy group and the like); more preferable are acetyloxy group and propionyloxy group.

The lower alkoxy group for R ¹ is
Examples thereof include linear or branched ones having 1 to 6 carbon atoms; preferably 1 carbon atom
4 to 4 groups (eg, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group); more preferably methoxy group ..

Examples of the lower alkylthio group for R ¹ include linear or branched ones having 1 to 6 carbon atoms; preferably those having 1 to 4 carbon atoms. (Eg, methylthio group, ethylthio group, n-propylthio group, i-propylthio group,
n-butylthio group, i-butylthio group, t-butylthio group, etc.); more preferably methylthio group.

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

Examples of the lower alkyl group for R ² include linear or branched ones having 1 to 6 carbon atoms; preferably 1 to 6 carbon atoms.
6 is preferable (eg, methyl group, ethyl group, n-
Propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, etc.); more preferred are methyl group, ethyl group and n-propyl group.

The cycloalkyl group for R ² is
Examples thereof include those having 3 to 8 carbon atoms; preferably those having 3 to 6 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.) A cyclopropyl group is more preferable.

R ³ is a lower haloalkoxy group, a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower alkylthio group, a nitro group, a lower haloalkyl group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower halo. Examples thereof include an alkylthio group and a hydroxyl group.

Examples of the lower haloalkoxy group for R ³ include linear or branched ones having 1 to 6 carbon atoms; preferably 1 to 4 carbon atoms. (Eg, difluoromethoxy group, trifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 3,3,3
-Trifluoropropyl group); and more preferably difluoromethoxy group and trifluoromethoxy group.

When R ³ is a lower haloalkoxy group, n can be an integer of 1 to 5, preferably 1. The position of the substituent is not particularly limited, but is preferably 3 or 4th place is good. When R ³ is a lower haloalkoxy group and a halogen atom, n is 2 to
An integer of 5 can be mentioned, but 2 is preferable; the position of the substituent is not particularly limited, but preferably 3 and 4-positions are preferable, and 4-position is a lower haloalkoxy group. The 3-position is preferably a halogen atom.

When R ³ is a lower haloalkoxy group or a lower alkoxy group, n may be an integer of 2 to 5, preferably 2; the position of the substituent is not particularly limited. , Preferably 3 and 4-positions, more preferably 4-position is a lower haloalkoxy group, and 3-position is an alkoxy group.

When R ³ is a lower haloalkoxy group or a lower alkyl group, n can be an integer of 2 to 5, preferably 2 to 4, more preferably 3; its substituents The position of is not particularly limited, but preferably 3-position, 4-position, 5-position and the like, more preferably 4-position is a lower haloalkoxy group, and 3 and 5-
It is preferred that the position is a lower alkyl group.

When R ³ is a hydrogen atom, n represents 5.

Examples of the lower alkyl group for R ³ include linear or branched ones having 1 to 6 carbon atoms; preferably 1 to 6 carbon atoms.
Four groups are preferable (for example, those described above as R ² ); more preferable are methyl group and t-butyl group. When R ³ is a lower alkyl group, n is 1
Although the integer of -5 can be mentioned, 1 or 2 is preferable; the position of the substituent is not particularly limited, but 2-position, 3-position, 4-position, 5-position and the like are preferable. ,
More preferably, when n is 1, 2-position and 3-position are preferable, and when n is 2, 3 and 4-position or 2 and 5-position are preferable.

The lower alkoxy group for R ³ is
Examples thereof include linear or branched ones having 1 to 6 carbon atoms; preferably 1 carbon atom
4 to 4 groups (for example, the groups described above as R ¹ ) are preferable; and a methoxy group is more preferable. R
^{When 3} is a lower alkoxy group, n may be an integer of 1 to 5, preferably 1. The position of the substituent is not particularly limited, but preferably 4-position.

Examples of the halogen atom for R ³ include those described above for R ¹ ; preferably a chlorine atom, a fluorine atom and a bromine atom. When R ³ is a halogen atom, n is 1 to
Although the integer of 5 can be mentioned, Preferably it is 1-4,
The position of the substituent is not particularly limited, but preferably 2-position, 3-position, 4-position in the case of chlorine atom and 2 in the case of fluorine atom. The -position, 3-position, 4-position and 6-position are preferable, and in the case of a bromine atom, 2-position and 4-position are preferable.

Examples of the lower haloalkylthio group for R ³ include those having the halogen atom described above as R ¹ and having a linear or branched alkyl group having 1 to 6 carbon atoms. The halogen atom is preferably a fluorine atom, and the alkyl group is preferably one having 1 to 4 carbon atoms (eg, difluoromethylthio group, trifluoromethylthio group, bromodifluoromethylthio group, 2-fluoroethylthio group, 2,2,2-trifluoroethylthio group,
3,3,3-trifluoropropylthio group); and more preferably a difluoromethylthio group. When R ³ is a lower haloalkylthio group, n may be an integer of 1 to 5, preferably 1; the position of the substituent is not particularly limited, but preferably 4-position. ..

When R ³ is a nitro group, n is 1 to
An integer of 5 can be mentioned, but 1 is preferable; the position of the substituent is not particularly limited, but 4-position is preferable.

Examples of the lower haloalkyl group for R ³ include linear or branched ones having 1 to 6 carbon atoms; preferably those having 1 to 4 carbon atoms. (E.g., trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group); and more preferably trifluoromethyl group. When R ³ is a lower haloalkyl group, n can be an integer of 1 to 5, preferably 1; the position of the substituent is not particularly limited, but preferably 2-position or 3-position. The place is good.

Examples of the lower alkylsulfinyl group for R ³ include linear or branched ones having 1 to 6 carbon atoms; preferably 1 to 4 carbon atoms. (Eg, methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, i-butylsulfinyl group, sec-butylsulfinyl group, t-butylsulfinyl group, etc. ); More preferably, methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group and n-butylsulfinyl group are preferable. When R ³ is a lower alkylsulfinyl group, n may be an integer of 1 to 5, preferably 1; the position of the substituent is not particularly limited, but preferably 4-position. ..

Examples of the lower alkylsulfonyl group for R ³ include linear or branched ones having 1 to 6 carbon atoms; preferably 1 to 4 carbon atoms. (For example, methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, i-butylsulfonyl group, sec-butylsulfonyl group, t-butylsulfonyl group, etc. ); More preferred are methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, and n-butylsulfonyl group. R
^{When 3} is a lower alkylsulfonyl group, n is 1
The integer of -5 can be mentioned, but 1 is preferable; the position of the substituent is not particularly limited, but 4-position is preferable.

R ⁴ and X are halogen atoms (eg R
¹ and the like described above). M represents an alkali metal. R ⁵ represents a lower acyloxy group (lower aliphatic carboxylic acid residue) corresponding to R ¹ .

[0036] In R ⁶ -Y, R ⁶ represents a lower alkyl group corresponding to R ^1; Y is an oxygen atom corresponding to R ^1,
Represents a sulfur atom. That is, R ⁶ -Y represents a lower alkoxy group or a lower alkylthio group corresponding to R ¹ .

As can be understood from the compound (I) of the present invention, since the compound (I) has an amino group and can easily form an acid addition salt, such a salt is also present. Included in the invention. Examples of acids that form acid addition salts 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 acid (methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), saccharin and the like.

As a preferred embodiment for producing the aralkylaminopyrimidine derivative represented by the above formula (I), in addition to the synthesis method 1 described as the second invention,
The following five production methods (synthesis methods 2 to 6) can be mentioned. [Synthesis Method 2] The following formula (I-1):

[0039]

[Chemical 7]

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

[0041]

[Chemical 8]

(In the formula, R ⁵ represents a lower acyloxy group.) In the above formula (I), R ¹ represents a lower acyloxy group, which is characterized by reacting with a lower aliphatic carboxylic acid. A method for producing an aralkylaminopyrimidine derivative. [Synthesis Method 3] The following formula (I-2):

[0043]

[Chemical 9]

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

[0045]

[Chemical 10]

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

[0047]

[Chemical 11]

(In the formula, R ² , R ³ and n have the same meanings as described above.) The aralkylaminopyrimidine derivative represented by the formula (I) is reacted with a fluorinating agent. ), A method for producing an aralkylaminopyrimidine derivative in which R ¹ represents a fluorine atom. [Synthesis Method 4] An aralkylaminopyrimidine derivative represented by the above formula (I-1) and the following formula (VI):

[0049]

[Chemical 12]

(In the formula, R ⁶ represents a lower alkyl group; Y
Represents an oxygen atom or a sulfur atom. ) An alcohol or mercaptan represented by the formula (1) is reacted with the aralkylaminopyrimidine derivative represented by the above formula (I) in which R ¹ is a lower alkoxy group or a lower alkylthio group. [Synthesis Method 5] An aralkylaminopyrimidine derivative represented by the above formula (I-1) and the following formula (VII):

[0051]

[Chemical 13]

An aralkylamino group in which R ¹ is a fluorine atom in the above formula (I) characterized by reacting with an alkali metal fluorine compound represented by the formula (wherein M represents an alkali metal). Process for producing pyrimidine derivative. The synthetic method of the compound (I) of the present invention will be described in more detail by the following synthetic methods 1 to 6. (Synthesis Method 1) As shown below, the compound (I) of the present invention is usually synthesized by reacting the starting compound (II) with the compound (III) in a solvent or without a solvent. However, it is preferable to react in the presence of a base in order to accelerate the reaction.

[0053]

[Chemical 14]

(In the formula, R ¹ , R ² , R ³ , X and n have the same meanings as described above.) The solvent is not particularly limited as long as it does not directly participate in this reaction, and for example, Chlorinated or unchlorinated aromatics such as benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane, Aliphatic and alicyclic hydrocarbons; diethyl ether,
Ethers such as tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; acetonitrile,
Nitriles such as propionitrile; organic bases such as triethylamine, pyridine, N, N-dimethylaniline; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; mixtures of the above solvents You can

The amount of the solvent used is the compound (I
The compound (II) can be used in a concentration range of 5 to 80% by weight, and preferably the compound (II) is used in a concentration of 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.); but organic bases are preferred.

Then, the amount of the base used depends on the amount of the compound (I
It can be used in an amount of 0.001 to 5 times by mole, preferably 0.8 to 5 times by mole, with respect to I).
The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent used, and preferably 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 raw material compound used is the amount of the compound (II
I) is 0.5 to 2 times mol, but preferably 0.8 to
It is preferably 1.5 times the molar amount.

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

[0060]

[Chemical 15]

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

The amount of the raw material compound used is 0.5 to 3 times mol, preferably 0.5 to 1.7 times mol of the compound (IX-1) with respect to the compound (VIII-1). Is good. Compound (V
III-3) is, for example, Journal of Chemical Society (JCS) 3478-3481 (195).
According to the method described in 5 years), it can be easily produced by carrying out as shown in the following formula.

[0063]

[Chemical 16]

(Wherein X has the same meaning as described above; R
Represents a lower alkyl group, a hydrogen atom, a hydroxyl group and 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) to (II-7) shown in Table 1.

The compound (III) used in the present invention is, for example,
J. Am. Chem. Soc. 70, 1315 (1948), Org. Syn. , Coll. , 2
Vol., P. 505 (1943) and the like, according to the method described in the following formula, the compound can be produced.

[0067]

[Chemical 17]

(In the formula, R ² , R ³ and n have the same meanings as described above.) Examples of the compound (III) include, for example, Tables 2 to 2.
Compounds (III) [compounds (III) ₁ to (III) consisting of the types of substituents corresponding to compounds 1 to 131 shown in 18
_It is called ₁₃₁ . For example, this compound (III) ₁ is a compound
In the formula represented by (III), R ² is a methyl group, and (R ³ ) _n
Means 4-OCHF ₂ . ] Can be mentioned.

Examples of the compound (I) are shown in Tables 2-1.
Compounds 1 to 131 shown in 8 [Compound 1 means that in the formula represented by the compound (I), R ¹ is a chlorine atom, R ² is a methyl group, and (R ³ ) _n is 4-OCHF _2. To do. ] Can be mentioned.

(Synthesis Method 2) Compound (I-2) [Compound (I) wherein R ¹ is a lower acyloxy group] is usually synthesized by compound (I-1)
The reaction can be carried out by reacting the compound with a compound (IV) in a solvent or without a solvent, but it is preferable to react in the presence of a base in order to accelerate the reaction.

[0071]

[Chemical 18]

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

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

The amount of the base used is the compound (I-
It can be used in a 1- to 5-fold molar quantity relative to 1),
It is preferably 2 to 5 times mol. The reaction temperature is
Although not particularly limited, it is within a temperature range from room temperature to the boiling point of the solvent used or less, and preferably 80 to 120 ° C.

The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 10 to 50 hours. As the compound (IV), a commercially available product can be used.

Target compound produced as described above
After completion of the reaction, (I-2) can be subjected to usual post-treatments such as extraction, concentration and filtration, and can be appropriately purified by a known means such as recrystallization and various chromatography if necessary.

Examples of the compound (I-2) are shown in Tables 2 to 1
Compounds 2, 9, 16, 17, 39, 40 shown in 8
50, 51, 57, 66, 68, 73, 77, 81, 8
It corresponds to 6,94,98,113,119,125 etc.
Each compound (I-2) consisting of the type of each substituent [Compound (I-
2)₂， (I-2)₉， (I-2)₁₆， (I-2)₁₇， (I-2)₃₉， (I-2)
₄₀， (I-2)_Fifty， (I-2)₅₁， (I-2)₅₇， (I-2)₆₆， (I-2)
 ₆₈， (I-2)₇₃， (I-2) ₇₇， (I-2)₈₁， (I-2)₈₆， (I-2)
 ₉₄， (I-2)₉₈， (I-2)₁₁₃， (I-2)₁₁₉， (I-2)
 ₁₂₅， (I-2)₁₃₃， (I-2)₁₃₉And so on. example
For example, this compound (I-2)₂Is a compound represented by the formula (I)
R in¹Is an acetyloxy group, R²Is a methyl group, (R
³)_nIs 4-OCHF₂Means that. ]
You can

(Synthesis Method 3) Compound (I-3) [compound (I) in which R ¹ is a hydroxyl group] is usually synthesized in the presence of a base.
It can be carried out by reacting 2) with compound (V) in a solvent.

[0079]

[Chemical 19]

(In the formula, R ² , R ³ , R ⁵ , M and n have the same meanings as described above.) As the solvent, in addition to the ethers, ketones and amides described in Synthesis Method 1, , Alcohols (for example, methanol, ethanol, propanol, butanol, etc.), water, and a mixture of the above solvents can be mentioned; preferably, a mixture of alcohols and water is preferable. The amount of the solvent used is the compound (I
-2) can be used in a concentration range of 5 to 80% by weight, but it is preferable to use the compound (I-2) in a concentration of 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 amount of the base used can be 1 to 5 times mol, preferably 2 to 5 times mol, of the compound (I-2).

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

As the compound (V), commercially available products can be used.

Target compound produced as described above
After completion of the reaction, (I-3) can be subjected to usual post-treatments such as extraction, concentration, filtration, etc., and if necessary, can be appropriately purified by a known means such as recrystallization or various chromatography.

Examples of the compound (I-3) are shown in Tables 2 to 1
Compounds 3, 10, 18, 46, 47, 5 shown in 8
2,53,58,61,63,67,69,74,7
8, 82, 87, 91, 95, 99, 114, 120,
Compounds (I-3) [compounds (I-3) ₃ , (I-3) ₁₀ , (I-3) ₁₈ ,
(I-3) ₄₆ , (I-3) ₄₇ , (I-3) ₅₂ , (I-3) ₅₃ , (I-3)
₅₈ , (I-3) ₆₁ , (I-3) ₆₃ , (I-3) ₆₇ , (I-3) ₆₉ , (I-3)
₇₄ , (I-3) ₇₈ , (I-3) ₈₂ , (I-3) ₈₇ , (I-3) ₉₁ , (I-3)
_{9 5} , (I-3) ₉₉ , (I-3) ₁₁₄ , (I-3) ₁₂₀ , (I-3) ₁₂₆ , (I-
3) ₁₃₀ , (I-3) ₁₃₄ , (I-3) _140, etc. For example, the compound (I-3) ₃ is represented by the compound (I), wherein R ¹ is a hydroxyl group, R ² is a methyl group, and (R ³ ) _n is 4-OCH.
It means F ₂ . ] Can be mentioned.

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

[0087]

[Chemical 20]

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

The fluorinating agent is represented by the following formula;

[0090]

[Chemical 21]

For example, diethylaminosulfur trifluoride (DAST) represented by can be used. And, the usage amount is 1 to the compound (I-3).
Although it can be used in a 5-fold molar amount, it is preferably in a 1- to 2-fold molar amount.

The reaction temperature is not particularly limited, but is within a temperature range from the ice cooling temperature to the boiling point of the solvent used or less, preferably room temperature to 40 ° C. The reaction time varies depending on the above-mentioned concentration and temperature, but can be usually 0.3 to 2 hours.

Target compound produced as described above
After completion of the reaction, (I-3) can be subjected to usual post-treatments such as extraction, concentration, filtration, etc., and if necessary, can be appropriately purified by a known means such as recrystallization or various chromatography.

Examples of the compound (I-4) are shown in Tables 2-1.
Compounds 4, 11, 19, 48, 49, 5 shown in 8
4,55,59,62,64,70,71,75,7
9, 83, 88, 92, 96, 100, 102-11
1,115-117, 121-123, 127-12
Each compound (I-4) consisting of each substituent type corresponding to 9,131, etc. [Compound (I-4) ₄ , (I-4) ₁₁ , (I-4) ₁₉ , (I-4)
₄₈ , (I-4) ₄₉ , (I-4) ₅₄ , (I-4) ₅₅ , (I-4) ₅₉ , (I-
4) ₆₂ , (I-4) ₆₄ , (I-4) ₇₀ , (I-4) ₇₁ , (I-4) ₇₅ , (I-
4) ₇₉ , (I-4) ₈₃ , (I-4) ₈₈ , (I-4) ₉₂ , (I-4) ₉₆ , (I-
4) ₁₀₀ , (I-4) ₁₀₂ ~ (I-4) ₁₁₁ , (I-4) ₁₁₅ ~ (I-4)
₁₁₇ , (I-4) ₁₂₁ ~ (I-4) ₁₂₃ , (I-4) ₁₂₇ ~ (I-4) _{1 29} ,
(I-4) ₁₃₁ , (I-4) ₁₃₅ ~ (I-4) ₁₃₇ , (I-4) ₁₄₁ ~ (I-4)
₁₄₃ , etc. For example, this compound (I-4) ₄ means that R ^{1 in the} formula represented by the compound (I) is a fluorine atom, R
² means a methyl group and (R ³ ) _n is 4-OCHF ₂ . ] Can be mentioned.

(Synthesis Method 5) Compound (I-5) [a compound in which R ¹ in compound (I) is a lower alkoxy group or a lower alkylthio group] is usually synthesized by compound (I-1) and compound (VI It can be carried out by reacting with) in a solvent or without solvent, but it is preferable to react in the presence of a base in order to promote the reaction.

[0096]

[Chemical formula 22]

(In the formula, R ² , R ³ , R ⁴ , R ⁶ , Y and n 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 70% by weight.

Examples of the base include the bases described in Synthesis Method 1, but inorganic bases are preferable. And, the amount of the base used is 1 to the compound (I-1).
It can be used in a 5-fold molar amount, but is preferably 1 to 3
It is preferable that the molar ratio is double.

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 be usually 0.3 to 2 hours.

The compound (VI) is used in an amount of 1 to 5 times, preferably 1 to 2 times the molar amount of the compound (VI) with respect to the compound (I-1). As the compound (VI), a commercially available product can be used.

Target compound produced as described above
After completion of the reaction, (I-5) can be subjected to usual post-treatments such as extraction, concentration and filtration, and can be appropriately purified by a known means such as recrystallization and various chromatography if necessary.

Examples of the compound (I-5) are shown in Tables 2 to 1
Compounds 6,7,13,14,21,22 shown in 8
Each compound (I-5) consisting of the kind of each corresponding substituent
(Compound (I-5)₆, (I-5)₇, (I-5)₁₃, (I-5)₁₄, (I-5)_{twenty one}, (I
-Five)_{twenty two}And so on. For example, this compound (I-5)₆And
R in the formula represented by compound (I)¹Is a methoxy group, R
²Is a methyl group, (R³)_nIs 4-OCHF₂That is
means. ] Can be mentioned.

(Synthesis Method 6) Compound (I-4) [Compound (I) wherein R ¹ is a fluorine atom] can be synthesized by the same method as in Synthesis Method 4
-1) and compound (VII) can be carried out by reacting with or without a solvent.

[0104]

[Chemical formula 23]

(In the formula, R ² , R ³ , R ⁴ , M and n have the same meanings as described above.) Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide and the like. Examples include amide agents; 1,3-dimethyl-2-imidazoline; dimethyl sulfoxide; sulfolane; and mixtures of the above solvents.

The amount of the solvent used is the compound (I-
The compound (1) can be used in a concentration range of 5 to 80% by weight, but it is preferable to use the compound (I-1) in a concentration of 10 to 70% by weight. Good.

Examples of the compound (VII) include alkali metal fluorine compounds, preferably cesium fluoride and potassium fluoride.

The amount of the compound used can be 1 to 5 times mol, preferably 1.2 to 3 times mol, of 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, or from room temperature to
40 ° C. is preferred. The reaction time varies depending on the above-mentioned concentration and temperature, but can be usually 1 to 8 hours.

Target compound produced as described above
After completion of the reaction, (I-4) can be subjected to usual post-treatments such as extraction, concentration and filtration, and can be appropriately purified by a known means such as recrystallization and various chromatography if necessary.

As the compound (I-4), the compounds described in Synthesis Method 4 can be mentioned.

The pests which can be controlled by the compound (I) of the present invention include agricultural and horticultural pests [for example, Hemiptera (Plants, leafhoppers, aphids, whiteflies, etc.), Lepidoptera (Beetle beetles). , Diamondback moth, leaf beetle, leaf moth, scabbard beetle, etc.), Coleoptera (Galloridae, Weevil, Chrysomelidae, Chafer, 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 downy mildew, rice blast, toma Epidemics, etc.) can be mentioned.

The pest control agent of the present invention is used for the remarkable insecticidal
It has acaricidal, nematicidal and bactericidal effects and contains one or more compounds (I) as active ingredients. Compound (I) can be used alone,
Usually, a carrier, a surfactant, a dispersant, an auxiliary agent, etc. are prepared by a conventional method (eg, a powder, an emulsion, a fine granule, a granule, a wettable powder, an oily suspension, a composition such as an aerosol). It is preferable to use.

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 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) out and the like.

Examples of surfactants and dispersants that can be used to improve the performance of the present agent such as adhesion to animals and plants, absorption improvement, drug dispersion, emulsification, and spread 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, carboxymethyl cellulose, polyethylene glycol, gum arabic or the like can be used as an auxiliary agent.

In the preparation 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.
The concentration of the active ingredient in the case where the compound (I) of the present invention is formulated is usually 1 to 50% by weight in an emulsion and 0.3 in a powder.
25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oils, usually 0.1 to 5% by weight for aerosols. is there.

These formulations 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.

[0118]

EXAMPLES The present invention will be specifically described below with reference to examples and examples. It should be noted that these examples do not limit the scope of the present invention. Reference Example 1 [Synthesis of starting compound (II)] (1) Synthesis of 6- (1-chloroethyl) -4,5-dichloropyrimidine [Compound (II-1)] 4,5-dichloro-6-ethylpyrimidine ( 270g)
Is dissolved in dichloromethane (750 ml), 30-35
Chlorine gas was blown in for 2 hours while being heated to ℃ and stirred. Nitrogen gas was blown into the reaction solution to remove excess chlorine gas dissolved therein. Then, the solvent was distilled off under reduced pressure, and the obtained residue was distilled under reduced pressure to obtain 240 g of a target product which was 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 reaction was completed by stirring at room temperature for 1 hour. 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 (Wako Gel C-200, eluted with chloroform) to obtain 1.3 g of the desired product as a pale yellow oily liquid.

(Physical properties) b. p. ^{229~231 ℃ · 1 H-NMR (} CDCl 3) δppm 1.64~1.81 (d-d, 3H), 5.84~6.
19 (dq, 1H), 8.92 (s, 1H)

(3) 5-chloro-4-fluoro-6- (1
Synthesis of -Fluoroethyl) pyrimidine [Compound (II-5)] 4,5-Dichloro-6- (1-fluoroethyl) pyrimidine (1.3 g) was added to N, N-dimethylformamide (1
0 ml) and dissolved in cesium fluoride (4.0 g)
Was added and stirred at room temperature for 1 hour and a half to complete the reaction. Cold water (10 ml) was added to the reaction solution, the separated oily substance 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, eluted with chloroform) to obtain 1.0 g of a target product as a pale yellow oily liquid.

(Physical properties) b. p. ^{192~194 ℃ · 1 H-NMR (} CDCl 3) δppm 1.66~1.82 (d-d, 3H), 5.85~6.
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 added 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, the separated oily substance 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 subjected to column chromatography (Wakogel C-20
0, toluene: ethyl acetate = 10: 1 elution) to obtain 5.2 g of the desired product as a pale yellow liquid.

(Physical properties) ¹ H-NMR (CDCl ₃ ) δppm 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) ) To tetrahydrofuran (50 ml)
Dissolved in 1N-sodium hydroxide aqueous solution (3
0 ml) was slowly added dropwise. After the dropping, the reaction was completed by further stirring for 1 hour at room temperature. Then, 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 oily substance was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 5: 1) to obtain 2.8 g of the desired product as a pale yellow liquid.

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

(6) Synthesis of Other Starting Compounds (II) in Table 1 Other starting compounds (II) in Table 1 were synthesized by the same method as in the above (1) to (5).

[0128]

[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) 5-chloro-6- (1-chloroethyl) -4- [1
-(4-Difluoromethoxyphenyl) ethylamino]
Synthesis of pyrimidine (Compound 1) 1- (4-Difluoromethoxyphenyl) ethylamine (3.8 g) and triethylamine (2.3 g) were dissolved in toluene (50 ml) to give 6- (1-chloroethyl).
Add 4,5-dichloropyrimidine (3.5 g) and add 5
Heated to reflux for 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, toluene: ethyl acetate = 9: 1 elution) to obtain 5.8 g of the target compound as a colorless oily liquid.

(2) 6- (1-acetoxyethyl) -5-
Synthesis of chloro-4- [1- (4-difluoromethoxyphenyl) ethylamino] pyrimidine (Compound 2) 5-chloro-6- (1-chloroethyl) -4- [1-
(4-Difluoromethoxyphenyl) ethylamino] pyrimidine (3.1 g) was dissolved in acetic acid (50 ml), then potassium acetate (3.0 g) and potassium carbonate (3.
0 g) was added and the mixture was heated under reflux for 30 hours. After 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, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wako Gel C-2
00, toluene: ethyl acetate = 3: 1 elution) to obtain 2.7 g of the target compound as a colorless oily liquid.
Obtained.

(3) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- [1- (4-difluoromethoxyphenyl) ethylamino] pyrimidine (Compound 3) 6-ethoxy- (1-acetoxyethyl ) -5-Chloro-4- [1- (4-difluoromethoxyphenyl) ethylamino] pyrimidine (2.0 g) in ethanol solution (1: 1 of ethanol and 10% aqueous sodium hydroxide solution).
Mixture. 20 ml) and stirred at room temperature for 3 hours.
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, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
The obtained oily substance was purified by column chromatography (Wakogel C-200, toluene: ethyl acetate = 1: 1 eluted) to obtain 1.6 g of the target compound as a colorless oily liquid.

(4) 5-chloro-6- (1-fluoroethyl) -4- [1- (4-difluoromethoxyphenyl)
Synthesis of ethylamino] pyrimidine (Compound 4) 5-chloro-6- (1-hydroxyethyl) -4- [1
-(4-Difluoromethoxyphenyl) ethylamino]
Pyrimidine (1.0 g) in dichloromethane (30 ml)
, Diethylaminosulfur trifluoride (0.4 g) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hour. 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, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The oily substance thus obtained was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 1: 1) to obtain 0.6 g of a target compound as a colorless oily liquid.

(5) Synthesis of 5-chloro-6- (1-methoxyethyl) -4- (1-phenylethylamino) pyrimidine (Compound 21) 5-chloro-6- (1-chloroethyl) -4- ( 1-Phenylethylamino) pyrimidine (1.11 g) was dissolved in methanol (20 ml), then sodium methoxide 28% methanol solution (1.3 g) was added, and 60
The mixture was stirred at 0 ° C for 13 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, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wakogel C-200, toluene:
Ethyl acetate = 10: 1 elution)
0.92 g of the target compound was obtained as a colorless oily liquid.

(6) Synthesis of 5-chloro-6- (1-methylthioethyl) -4- (1-phenylethylamino) pyrimidine (Compound 22) 5-chloro-6- (1-chloroethyl) -4- ( 1-Phenylethylamino) pyrimidine (1.20 g) was dissolved in methanol (30 ml), then a 15% aqueous solution of sodium methanethiol salt (2.89 g) was added, and the mixture was stirred at room temperature 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, dried over anhydrous sodium sulfate, and 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 0.8 g of the target compound as a colorless oily liquid.

(7) 4-benzylamino-5-chloro-6
Synthesis of-(1-fluoroethyl) pyrimidine (Compound 48) 4-Benzylamino-5-chloro-6- (1-chloroethyl) pyrimidine (2.8 g) was dissolved in N, N-dimethylformamide (30 ml), Cesium fluoride (3.0 g) was added, and the mixture was stirred at 120 to 140 ° C. for 12 hours. After completion of the reaction, water was added, and then the target compound was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wako Gel C
-200, toluene: ethyl acetate = 9: 1 elution) to give 1.1 of the target compound as a colorless oily liquid.
3 g was obtained.

(8) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- [1- (4-chlorophenyl) cyclopropylmethylamino] pyrimidine (Compound 83) 1- (4-chlorophenyl) cyclopropyl Methylamine (1.8 g) and triethylamine (1.3 g) were dissolved in toluene (30 ml), and 4,5-dichloro-6- (1-fluoroethyl) pyrimidine (2.0
g) was added and the mixture was heated under reflux for 5 hours. After completion of the reaction, water was added, and then the target compound was extracted with ethyl acetate. The extract was 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 (Wako Gel C-200, eluted with toluene: ethyl acetate = 8: 1) to obtain 1.8 g of the target compound as a colorless oily liquid.

(9) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- [1- (4-trifluoromethoxyphenyl) ethylamino] pyrimidine (Compound 87) 4- [1- (4- Trifluoromethoxyphenyl) ethylamine (2.1 g) and triethylamine (1.3 g)
And are dissolved in toluene (30 ml) and stirred under 4,5-
Dichloro-6- (1-hydroxyethyl) pyrimidine (2.0 g) was added and the mixture was heated under reflux for 5 hours. After completion of the reaction, water was added, and then the target compound was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by column chromatography (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 2.4 g of the target compound as a colorless oily liquid.

(10) 6- (1-acetoxyethyl) -5-
Synthesis of chloro-4- [1- (4-methylthiophenyl) ethylamino] pyrimidine (Compound 98) 1- (4-methylthiophenyl) ethylamine (1.8
g) and triethylamine (1.3 g) together with toluene (3
0 ml), 6- (1-acetoxyethyl) -4,5-dichloropyrimidine (2.4 g) was added with stirring, and the mixture was heated under reflux for 5 hours. After completion of the reaction, water was added, and then the target compound was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wakogel C-200, toluene: ethyl acetate =
Purification by elution (10: 1) gave 2.8 g of the desired compound as a colorless oily liquid.

(11) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- [1- (4-methylthiophenyl) ethylamino] pyrimidine (Compound 99) 6- (1-acetoxyethyl) -5 -Chloro-4- [1
-(4-Methylthiophenyl) ethylamino] pyrimidine (5.5 g) in ethanol solution (ethanol and 10%
1: 1 mixture of sodium hydroxide. 100 ml) and stirred at room temperature for 3 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, and then the target compound was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and 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: 1) to obtain 4.7 g of the target compound as colorless crystals.

(12) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- [1- (4-methylthiophenyl) ethylamino] pyrimidine (Compound 100) 5-chloro-6- (1-hydroxy Ethyl) -4- [1
-(4-Methylthiophenyl) ethylamino] pyrimidine (4.7 g) was dissolved in dichloromethane (80 ml), diethylaminosulfur trifluoride (2.6 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 mixture was extracted with chloroform. The extract was 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 = 10: 1) to obtain 3.8 g of the target compound as a pale yellow oil.

(13) 5-chloro-6- (1-fluoroethyl) -4- [1- (4-methylsulfenylphenyl)
Ethylamino] pyrimidine (Compound 103) and 5-chloro-6- (1-fluoroethyl) -4- [1- (4-
Synthesis of Methylsulfonylphenyl) ethylamino] pyrimidine (Compound 104) 5-chloro-6- (1-fluoroethyl) -4- [1-
(4-methylthiophenyl) ethylamino] pyrimidine (2.6 g) was dissolved in dichloromethane (50 ml),
Metachloroperbenzoic acid (1.6 g) was added, and the mixture was stirred at room temperature for 1 hr. After completion of the reaction, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with chloroform. The extract was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by column chromatography (Wakogel C-200, eluted with ethyl acetate) to give the target compound (compound 10) as colorless crystals.
0.8 g of 4) and 1.4 g of the target compound (compound 103) which is a colorless rubbery substance were obtained.

(14) Synthesis of Other Target Compound (I) Other target compound (I) was synthesized according to the method described in (1) to (13) above. The compounds synthesized as described above are shown in Tables 2 to 19, and the compounds 4, 10, 103, 11
Table 20 shows the physical properties of 1 and 122.

[0143]

[Table 2]

[0144]

[Table 3]

[0145]

[Table 4]

[0146]

[Table 5]

[0147]

[Table 6]

[0148]

[Table 7]

[0149]

[Table 8]

[0150]

[Table 9]

[0151]

[Table 10]

[0152]

[Table 11]

[0153]

[Table 12]

[0154]

[Table 13]

[0155]

[Table 14]

[0156]

[Table 15]

[0157]

[Table 16]

[0158]

[Table 17]

[0159]

[Table 18]

[0160]

[Table 19]

[0161]

[Table 20]

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 lignin sulfonate were uniformly mixed, and then a small amount of water was added and kneaded, then granulated and dried to obtain a granule.

(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 Co., Ltd.)
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 Kasei Co., Ltd.) were added and mixed uniformly to obtain an emulsion. ..

(4) Preparation of powder preparation 5 parts by weight of compound 1, 50 parts by weight of talc and 4 parts of kaolin
A powder was obtained by uniformly mixing 5 parts by weight.

Example 3 [Efficacy test] (1) Efficacy test against Spodoptera litura Each of the wettable powders of the compound (I) shown in Tables 2 to 19 prepared according to Example 2 was mixed with a surfactant (0.01%). Was diluted to 500 ppm with water containing water, and soybean true leaves were dipped in each of these chemical solutions for 30 seconds, placed in each plastic cup one by one and air-dried. In each of these cups, 10 Spodoptera litura (2nd instar larvae) were released, covered with the lids, allowed to stand in a constant temperature room at 25 ° C., and after 2 days, the number of live and dead insects in each cup was counted to determine the insecticidal rate. As a comparative example, European Patent Laid-Open Publication No. 470600 (JP-A-4-230670).
No.) described in the following formula (X);

[0167]

[Chemical formula 24]

The compound of formula (I) was formulated and tested in the same manner as the compound of the present invention. The insecticidal effect is evaluated in four stages (A: 100%, B: 99 to 8) depending on the range of the insecticidal rate.
0%, C: 79-60%, D: 59% or less).
The results are shown in Table 21.

[0169]

[Table 21]

(2) Efficacy test against brown planthopper Each wettable powder of compound (I) shown in Tables 2 to 19 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 brown planthopper, 10 instars, 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, and after 4 days, the number of live and dead insects in each glass cylinder was counted and the insecticidal rate was determined. I asked. The results of the evaluation of insecticidal effect are
Table 22 shows the comparative examples of the compound (X) described in (1) and the evaluation method in four stages.

[0171]

[Table 22]

(3) Efficacy test against adult females of the genus Nymphalidae Each of the wettable powders of the compound (I) shown in Tables 2 to 19 prepared according to Example 2 was treated with water containing a surfactant (0.01%) to give 300 ppm. Each kidney bean leaf piece (diameter: 2)
0 mm) was immersed for 10 seconds each. Next, these leaf pieces were left in a constant temperature room at 25 ° C., and three days later, the number of live and dead insects in each leaf piece was counted to determine the miticidal rate. The results of evaluation of the acaricidal effect are shown in Table 23 together with the comparative example of the compound (X) described in (1) above by a 4-step evaluation method.

[0173]

[Table 23]

(4) Efficacy test against sweet potato nematode Each wettable powder of the compound (I) shown in Tables 2 to 19 prepared according to Example 2 was diluted with water to 20 ppm. 0.5 ml of this drug solution and an aqueous solution containing 30 to 40 larvae of the second stage sweet potato root-knot nematode (within 24 hours of hatching)
ml and was placed in a test tube. Next, it was allowed to stand 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 × field of view) to determine the nematicidal rate. The evaluation of the nematicidal effect is divided into four levels (A: 10
0-90%, B: 89-80%, C: 79-60%,
D: 59% or less). The results of evaluation of the nematicidal effect are shown in Table 24 together with the comparative example of the compound (X) described in (1) above.

[0175]

[Table 24]

(5) Control efficacy test against barley powdery mildew (preventive effect) Ten barleys (cultivar: black wheat) were grown in a plastic flower pot with a diameter of 6 cm, and seedlings of 1.5 leaf stage were grown. In addition, each wettable powder of the compound (I) shown in Tables 2 to 19 prepared according to Example 2 was added with a surfactant (0.01%).
Each of the chemical solutions was diluted to 500 ppm with water containing water and sprayed in an amount of 20 ml per pot. These were cultivated in a glass greenhouse for 2 days, and then, the barley powdery mildew fungus sporulated spores were collected from the diseased leaves, and sprinkled evenly over each plant to inoculate. Next, these were grown in a glass greenhouse for one week, and the degree of barley powdery mildew lesions appearing on each first leaf was investigated. The evaluation of the bactericidal effect was carried out in 6 stages (0: the entire 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 lesions). These results are shown in Table 25.
Shown in.

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[Table 25]

(6) Control Efficacy Test Against Wheat Leaf Rust (Preventive Effect) 10 wheats (cultivar: Kobushi-komugi) were cultivated in a plastic flower pot with a diameter of 6 cm, and seedlings of 1.5 leaf stage were grown. A wettable powder of the compound (I) shown in Tables 2 to 19 prepared according to Example 2 was mixed with a surfactant (0.01
%) And dilute it to 500ppm with 2% per pot.
Sprayed with 0 ml. After spraying, cultivate in a glass greenhouse for 2 days, and then spore suspension of wheat leaf rust (7 x 10
⁴ / ml) was uniformly spray-inoculated on the plants. After inoculation, 1
After growing in a glass greenhouse for a week, the extent of wheat leaf rust lesions on the first leaf was investigated. The results are shown in Table 26 by the 6-step evaluation method described in (5) above.

[0179]

[Table 26]

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INDUSTRIAL APPLICABILITY The novel aralkylaminopyrimidine derivative of the present invention is a useful pesticide having excellent pest control effects such as excellent insecticidal, acaricidal, nematicidal and bactericidal properties.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Nakamoto 5 1978, Kogushi, Ube City, Yamaguchi Prefecture Ube Kosan Co., Ltd. Ube Laboratory

Claims (3)

[Claims] 1. The following formula: (Wherein R ¹ represents a halogen atom, a lower acyloxy group, a hydroxyl group, a lower alkoxy group or a lower alkylthio group; R ² represents a lower alkyl group, a hydrogen atom or a cycloalkyl group; R ³ represents a lower haloalkoxy group, Hydrogen atom,
Represents a lower alkyl group, a lower alkoxy group, a halogen atom, a lower alkylthio group, a nitro group, a lower haloalkyl group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower haloalkylthio group or a hydroxyl group; n is 1
Represents an integer of 5; ) An aralkylaminopyrimidine derivative represented by: 2. The following formula: (In the formula, 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 , R ³ and n have the same meanings as described in claim 1.) Reacted with an aralkylamine represented by formula (I), which is represented by formula (I). Process for producing aralkylaminopyrimidine derivative. 3. A pest control agent containing the aralkylaminopyrimidine derivative represented by the formula (I) according to claim 1 as an active ingredient.