JP3074658B2 - Aralkylaminopyrimidine 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 aralkylaminopyrimidine derivative which is useful as an insecticide, acaricide, nematocide, fungicide and the like.

[0002]

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

[0003]

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

[0004]

Means for Solving the Problems As a result of investigations to solve the above problems, the present inventors have found that novel aralkylaminopyrimidine derivatives are useful as insecticides, acaricides, nematocides, fungicides and the like. The present invention was found to have remarkable pest control activity as a pesticidal agent, and completed the present invention. That is, the present invention is as follows. The first invention provides the following formula (I):

[0005]

Embedded image

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; and R ³ represents a lower halo group. Alkoxy 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 haloalkylthio group or a hydroxyl group; Represents an integer. )). In the compound (I) of the present invention, the carbon atom marked with * is an asymmetric carbon atom, and any optical isomer, racemate, diastereomer compound or a mixture thereof is included in the present invention. . A second invention provides the following formula (II):

[0007]

Embedded image

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

[0009]

Embedded image

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

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

Hereinafter, the present invention will be described in detail. Novel aralkylaminopyrimidine derivatives (I) [Compounds (I-1), (I-2), (I-3), (I-
4) and (I-5)], and the compound (I
R ¹ , 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 and a lower alkylthio group.

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.

The lower acyloxy group for R ¹ includes, for example, those having a total of 2 to 6 carbon atoms and having a linear or branched alkyl group; Two to four 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.

As the lower alkoxy group for R ¹ ,
For example, straight or branched ones having 1 to 6 carbon atoms can be mentioned; preferably 1 to 6 carbon atoms.
Preferably 4 to 4 (for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group); more preferably methoxy group. .

As the lower alkylthio group for R ^1, there can be mentioned, for example, a linear or branched one having 1 to 6 carbon atoms; preferably a lower alkylthio group having 1 to 4 carbon atoms. (Eg, methylthio, ethylthio, n-propylthio, i-propylthio,
an n-butylthio group, an i-butylthio group, a t-butylthio group, etc.); more preferably a methylthio group.

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

The lower alkyl group for R ² includes, for example, a linear or branched one having 1 to 6 carbon atoms; preferably 1 to 6 carbon atoms.
Six (eg, methyl, ethyl, n-
Propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, etc.); more preferably, methyl group, ethyl group and n-propyl group.

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

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.

The lower haloalkoxy group for R ³ includes, for example, a linear or branched one having 1 to 6 carbon atoms; preferably a lower haloalkoxy group having 1 to 6 carbon atoms. (For example, difluoromethoxy group, trifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 3,3,3
-Trifluoropropyl group and the like); more preferably a difluoromethoxy group and a trifluoromethoxy group.

In the case where R ³ is a lower haloalkoxy group, n may be an integer of 1 to 5, preferably 1; the position of the substituent is not particularly limited, but is preferably 3 or 4-position is good. When R ³ is a lower haloalkoxy group and a halogen atom, n is 2 to
An integer of 5 can be cited, preferably 2; the position of the substituent is not particularly limited, but is preferably 3 and 4-position, more preferably 4-position is a lower haloalkoxy group. , 3-position is preferably a halogen atom.

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

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

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

The lower alkyl group for R ³ includes, for example, a linear or branched one having 1 to 6 carbon atoms; preferably 1 to 6 carbon atoms.
Four are preferred (for example, those described above as R ² ); more preferred are a methyl group and a t-butyl group. When R ³ is a lower alkyl group, n is 1
Integers from 5 to 5 can be mentioned, preferably 1 or 2; the position of the substituent is not particularly limited, but preferably 2-position, 3-position, 4-position, 5-position, etc. ,
More preferably, when n is 1, the 2- and 3-positions are good, and when n is 2, the 3- and 4-positions or the 2- and 5-positions are good.

As the lower alkoxy group for R ³ ,
For example, straight or branched ones having 1 to 6 carbon atoms can be mentioned; preferably 1 to 6 carbon atoms.
4 to 4 are preferred (for example, those described above as R ¹ ); more preferably a methoxy group. R
^When n 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 is preferably 4-position.

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

The lower haloalkylthio group for R ³ includes, for example, those having a halogen atom described above as R ¹ and having a linear or branched alkyl group having 1 to 6 carbon atoms. Preferably, the halogen atom is a fluorine atom, and the alkyl group is a group having 1 to 4 carbon atoms (for example, a difluoromethylthio group, a trifluoromethylthio group, a bromodifluoromethylthio group, 2-fluoroethylthio group, 2,2,2-trifluoroethylthio group,
3,3,3-trifluoropropylthio group and the like); 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 is preferably 4-position. .

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

As the lower haloalkyl group for R ^3, there can be mentioned, for example, a linear or branched one having 1 to 6 carbon atoms; preferably a lower haloalkyl group having 1 to 4 carbon atoms. (For example, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, etc.); 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 is preferably 2-position or 3-position. Good place.

As the lower alkylsulfinyl group for R ^3, there can be mentioned, for example, a linear or branched one having 1 to 6 carbon atoms; preferably a lower alkylsulfinyl group having 1 to 6 carbon atoms. (Eg, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, i-propylsulfinyl, n-butylsulfinyl, i-butylsulfinyl, sec-butylsulfinyl, t-butylsulfinyl, etc.) And more preferably a methylsulfinyl group, an ethylsulfinyl group, an n-propylsulfinyl group, and an n-butylsulfinyl group. When R ³ is a lower alkylsulfinyl group, n can be an integer of 1 to 5, preferably 1; the position of the substituent is not particularly limited, but is preferably 4-position. .

The lower alkylsulfonyl group for R ³ includes, for example, a linear or branched one having 1 to 6 carbon atoms; preferably a lower alkylsulfonyl group having 1 to 6 carbon atoms. (E.g., methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl, i-butylsulfonyl, sec-butylsulfonyl, t-butylsulfonyl, etc.) And more preferably a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, and an n-butylsulfonyl group. R
^{When 3} is a lower alkylsulfonyl group, n is 1
Integers from 5 to 5 can be mentioned, preferably 1; the position of the substituent is not particularly limited, but is preferably 4-position.

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

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

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

[0039]

Embedded image

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

[0041]

Embedded image

(Wherein, R ⁵ represents a lower acyloxy group). In the above formula (I), R ¹ is a lower acyloxy group. For producing aralkylaminopyrimidine derivatives. [Synthesis method 3] The following formula (I-2):

[0043]

Embedded image

(Wherein R ² , R ³ , R ⁵ and n are as defined above) and an aralkylaminopyrimidine derivative represented by the following formula (V):

[0045]

Embedded image

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

[0047]

Embedded image

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

[0049]

Embedded image

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

[0051]

Embedded image

Wherein aralkylamino wherein R ¹ is a fluorine atom in the above formula (I) is reacted with an alkali metal fluorine compound represented by the formula (wherein M represents an alkali metal). A method for producing a pyrimidine derivative. The method for synthesizing compound (I) of the present invention will be described in more detail by the following synthesis methods 1 to 6. (Synthesis Method 1) The synthesis of compound (I) of the present invention can be usually carried out by reacting compound (II) as a raw material with compound (III) in a solvent or without solvent as shown below. Although it is possible, the reaction is preferably performed in the presence of a base in order to accelerate the reaction.

[0053]

Embedded image

(Wherein R ¹ , R ² , R ³ , X and n are as defined above). The solvent is not particularly limited as long as it does not directly participate in the reaction. Chlorinated or unchlorinated aromatics, such as benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane, Aliphatic or alicyclic hydrocarbons; diethyl ether,
Ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; 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; Can be.

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

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

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

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

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

[0060]

Embedded image

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

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

[0063]

Embedded image

(Wherein X has the same meaning as described above;
Represents a lower alkyl group, a hydrogen atom, a hydroxyl group and a halogen atom. After completion of the reaction, the target compound (II) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, re-crystallized, and various means known in the art such as chromatography. And can be appropriately purified.

Examples of the compound (II) include the starting compounds (II-1) to (II-7) shown in Table 1.

Compound (III) used in the present invention is, for example,
J. Am. Chem. Soc. 70, 1315 (1948), Org. Syn. , Coll. , 2
Volume, p. 505 (1943), etc., according to the following formula.

[0067]

Embedded image

(Wherein R ² , R ³ and n have the same meanings as described above).
Compounds (III) [Compounds (III) ₁ to (III)] consisting of the types of substituents corresponding to Compounds 1 to 131 shown in 18
_{Called 131} . For example, the compound (III) ₁ is a compound
R ^{2 in the} formula (III) is a methyl group, (R ³ ) _n
Means that but a 4-OCHF _2. ].

Compounds (I) include, for example, those described in Tables 2-1
Compounds 1 to 131 shown in 8 [Compound 1 means that R ^{1 in the} formula represented by compound (I) is a chlorine atom, R ² is a methyl group, and (R ³ ) _n is 4-OCHF _2. I do. ].

(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 the compound (IV) in a solvent or in the absence of a solvent, but the reaction is preferably carried out in the presence of a base to promote the reaction.

[0071]

Embedded image

(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, proprionic acid, etc. And a mixture thereof; N, N-dimethylformamide and the same aliphatic carboxylic acid as the acyloxy group to be introduced are preferred.

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

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

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

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

Compounds (I-2) include, for example, those described in Tables 2-1
Compounds 2, 9, 16, 17, 39, 40, and
50, 51, 57, 66, 68, 73, 77, 81, 8
6, 94, 98, 113, 119, 125, etc.
Compound (I-2) consisting of each type of substituent (Compound (I-
2)_Two, (I-2)₉, (I-2)₁₆, (I-2)₁₇, (I-2)₃₉, (I-2)
₄₀, (I-2)₅₀, (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
If this compound (I-2)_TwoIs a compound represented by the formula (I)
R in¹Is an acetyloxy group, R^TwoIs a methyl group, (R
^Three)_nIs 4-OCHF_TwoMeans that ]
Can be

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

[0079]

Embedded image

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

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

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

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

The target compound produced as described above
After completion of the reaction, (I-3) is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and can be appropriately purified as necessary by known means such as recrystallization and various types of chromatography.

Compounds (I-3) include, for example, those described in Tables 2-1
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,
Each compound (I-3) consisting of each type of substituent corresponding to 126, 130, etc. [Compound (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 a compound represented by the formula (I) wherein R ¹ is a hydroxyl group, R ² is a methyl group, and (R ³ ) _n is 4-OCH
Means that it is F _2. ].

(Synthesis Method 4) Compound (I-4) [Compound (I) wherein R ¹ is a fluorine atom] is usually synthesized by compound (I-3) and a fluorinating agent in a solvent or The reaction can be performed in the absence of a solvent.

[0087]

Embedded image

(Wherein R ² , R ³ and n have the same meanings as described above). As the solvent, the chlorinated or non-chlorinated aromatic, aliphatic, or alicyclic ring described in Synthesis Method 1 is used. Mention may be made of hydrocarbons of the formula, ethers and mixtures of said solvents. The amount of the solvent used is determined by the amount of the compound (I
The compound (I-3) can be used in a concentration range of from 5 to 80% by weight, but preferably the compound (I-3) is used in a concentration range of from 10 to 70% by weight. Is good.

As the fluorinating agent, the following formula:

[0090]

Embedded image

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

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

The target compound produced as described above
After completion of the reaction, (I-3) is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and can be appropriately purified as necessary by known means such as recrystallization and various types of chromatography.

Compounds (I-4) include, for example, those described 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
Compounds (I-4) [Compounds (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, the compound (I-4) ₄ is a compound represented by the formula (I) wherein R ¹ is a fluorine atom, R
² means a methyl group, and (R ³ ) _n means 4-OCHF ₂ . ].

(Synthesis Method 5) Compound (I-5) [Compound (I) wherein R ¹ is a lower alkoxy group or a lower alkylthio group] is usually synthesized by compound (I-1) and compound (VI ) In a solvent or in the absence of a solvent, but is preferably performed in the presence of a base to accelerate the reaction.

[0096]

Embedded image

(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 those 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 range of 5 to 80% by weight. It is good to use it so that it may be about 70% by weight.

As the base, the bases described in the synthesis method 1 can be mentioned, but an inorganic base is preferred. The amount of the base used is 1 to 1 with respect to compound (I-1).
It can be used in a molar amount of 5 times, preferably 1 to 3 times.
It is preferable that the amount is twice as much.

The reaction temperature is not particularly limited, but is in the range of from room temperature to the boiling point of the solvent used, and is 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 (VI) to be used is 1 to 5 moles, preferably 1 to 2 moles, relative to compound (I-1). As the compound (VI), a commercially available product can be used.

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

As the compound (I-5), for example, the compounds shown in Tables 2-1
The compounds 6, 7, 13, 14, 21, 22 and 22 shown in FIG.
Each compound consisting of each type of substituent corresponding to (I-5)
(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)₆What is
R in the formula represented by the compound (I)¹Is a methoxy group, R
^TwoIs a methyl group, (R^Three)_nIs 4-OCHF_TwoThat is
means. ].

(Synthesis Method 6) Compound (I-4) [Compound (I) wherein R ¹ is a fluorine atom]
-1) and compound (VII) in a solvent or without solvent.

[0104]

Embedded image

(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. Amide agents; 1,3-dimethyl-2-imidazoline; dimethyl sulfoxide; sulfolane; mixtures of the above solvents.

The amount of the solvent used is determined by the amount of the compound (I-
The compound (I) can be used such that the concentration of 1) is in the range of 5 to 80% by weight. Preferably, the compound (I-1) is used in a concentration of 10 to 70% by weight. Good.

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

The amount of use can be 1 to 5 moles per mole of Compound (I-1), but preferably 1.2 to 3 moles.

The reaction temperature is not particularly limited, but is in the range of from room temperature to the boiling point of the solvent used, and is
40 ° C. is preferred. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 1 to 8 hours.

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

As the compound (I-4), each compound described in the synthesis method 4 can be exemplified.

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

The pesticidal composition of the present invention has a remarkable insecticidal property.
It has an acaricidal / nematocidal / bactericidal effect and contains at least one compound (I) as an active ingredient. Compound (I) can be used alone,
Usually, a carrier, surfactant, dispersant, adjuvant, etc. are blended by a usual method (for example, prepared as a composition such as powder, emulsion, fine granule, granule, wettable powder, oily suspension, aerosol, etc.) Is preferably used.

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea, etc .; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene, etc.) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Examples of surfactants and dispersants which can be used for improving the performance of the agent, such as adhesion to animals and plants, improvement in absorption, dispersion, emulsification and spreading of drugs, include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent.

In the preparation of the present preparation, the above-mentioned carrier, surfactant, dispersant and auxiliary can be used alone or in appropriate combination, respectively, according to the respective purposes.
When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in the emulsion, and usually from 0.3 to 0.3 in the powder.
25 to 25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. is there.

These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on the foliage of plants, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0118]

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 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) and 30-35
C., and chlorine gas was blown in for 2 hours while stirring. Nitrogen gas was blown into the reaction solution to remove dissolved excess chlorine gas. Then, the solvent was distilled off under reduced pressure, and the obtained residue was distilled under reduced pressure to obtain 240 g of the target substance as a pale yellow liquid.

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

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

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

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

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

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

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

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

(6) Synthesis of other starting compounds (II) in Table 1 In the same manner as in the above (1) to (5), other starting compounds (II) in Table 1 were synthesized.

[0128]

[Table 1]

Example 1 [Synthesis of Compound (I)] Using the starting compound (II) obtained in Reference Example 1, the target compound (I) was synthesized. (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), and 6- (1-chloroethyl) was dissolved.
-4,5-Dichloropyrimidine (3.5 g) was added and 5
Heated to reflux for an hour. After completion of the reaction, the solvent was distilled off under reduced pressure, the target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
The obtained oil was purified by column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 9: 1) to obtain 5.8 g of the target compound as a colorless oil.

(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), and then potassium acetate (3.0 g) and potassium carbonate (3.
0 g) and 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 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-2).
Then, 2.7 g of the target compound as a colorless oily liquid was obtained.
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 an ethanol solution (1: 1 of ethanol and a 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 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, elution with toluene: ethyl acetate = 1: 1) to give 1.6 g of the target compound as a colorless oil.

(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)
And diethylaminosulfur trifluoride (0.4 g) was added dropwise under ice-cooling, followed by stirring at room temperature for 1 hour. After completion of the reaction, 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, toluene: ethyl acetate = 1: 1 elution) to obtain 0.6 g of the target compound as a colorless oil.

(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), and then a 28% methanol solution of sodium methoxide (1.3 g) was added.
Stirred at 13 ° 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 and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-200, toluene:
(Ethyl acetate = 10: 1 elution).
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 methanethiol sodium 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 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) to give 0.8 g of the target compound as a colorless oil.

(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 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 = 9: 1) to give the target compound as a colorless oily liquid in 1.
3 g were 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 and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, toluene: ethyl acetate = 8: 1 elution) to obtain 1.8 g of the target compound as a colorless oil.

(9) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- [1- (4-trifluoromethoxyphenyl) ethylamino] pyrimidine (compound 87) (Trifluoromethoxyphenyl) ethylamine (2.1 g) and triethylamine (1.3 g)
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 and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 2.4 g of the target compound as a colorless oil.

(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) in 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 and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-200, toluene: ethyl acetate =
(10: 1 elution) to obtain 2.8 g of the target 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 and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, toluene: ethyl acetate = 1: 1 elution) 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 hour. After the reaction was completed, ice water (30 ml) was added, and the mixture 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 = 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 hour. After completion of the reaction, a saturated aqueous solution of sodium hydrogen carbonate was added, and the mixture 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 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) as a colorless rubber were obtained.

(14) Synthesis of Other Target Compound (I) Other target compound (I) was synthesized according to the methods described in the above (1) to (13). 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 ligninsulfonate were uniformly mixed, then kneaded by adding a small amount of water, and then granulated and dried to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 1, 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neoperex powder (trade name, manufactured by Kao Corporation) and Demol (product) Name; manufactured by Kao Corporation)
Then, it was pulverized to obtain a wettable powder.

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

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

Example 3 [Efficacy test] (1) Efficacy test for Spodoptera litura [0166] Each wettable powder of compound (I) shown in Tables 2 to 19 prepared according to Example 2 was treated with a surfactant (0.01%) , And soybean leaves were immersed in each of these chemical solutions for 30 seconds, placed one by one in each plastic cup, and air-dried. In each of these cups, ten cutworm armyworms (2nd instar larvae) were released, covered, left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate. As a comparative example, European Patent Publication No. 470600 (JP-A-4-230670)
No.) described in the following formula (X);

[0167]

Embedded image

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

[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 respective glass cylinders. Next, 10 brown hoppers, 4th instar larvae, were released into each of these glass cylinders, covered with a porous lid, and allowed to stand in a constant temperature room at 25 ° C. I asked. The results of the evaluation of the insecticidal effect
The results are shown in Table 22 along with the comparative examples of the compound (X) described in (1) by a four-step evaluation method.

[0171]

[Table 22]

(3) Efficacy test against adult female spider mite (Acari: Tetranychida) Each wettable powder of compound (I) shown in Tables 2 to 19 prepared according to Example 2 was mixed with water containing a surfactant (0.01%) at 300 ppm. , And each of these liquid chemicals was infested with 10 adult female spider mites, kidney beans (diameter 2).
0 mm) for 10 seconds. Next, each leaf piece was left in a constant temperature room at 25 ° C., and after 3 days, the number of live and dead insects in each leaf piece was counted to determine the acaricidal rate. The results of the evaluation of the acaricidal effect are shown in Table 23 along with the comparative examples of the compound (X) described in the above (1) by a four-step evaluation method.

[0173]

[Table 23]

(4) Efficacy test on sweet potato nematode Each wettable powder of compound (I) shown in Tables 2 to 19 prepared according to Example 2 was diluted to 20 ppm with water. 0.5 ml of this drug solution and an aqueous solution containing 30 to 40 head larvae of the sweet potato root-knot nematode (within 24 hours of hatching)
ml was placed in a test tube. Next, it was left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects was counted under a microscope (40-fold visual field) to determine the necrotic nematode rate. The nematicidal effect was evaluated in four stages (A: 10) according to the range of the nematicidal rate.
0-90%, B: 89-80%, C: 79-60%,
D: 59% or less). The results of the evaluation of the nematicidal effect are shown in Table 24 together with the comparative examples of the compound (X) described in the above (1).

[0175]

[Table 24]

(5) Test for controlling efficacy against barley powdery mildew (preventive effect) 10 barleys (cultivar: black wheat) are grown in plastic plant pots having a diameter of 6 cm per pot, and seedlings of 1.5-leaf stage are grown. Then, each wettable powder of the compound (I) shown in Tables 2 to 19 prepared according to Example 2 was added to a surfactant (0.01%).
And diluted with water containing 500 ppm to each, and each of these chemicals was sprayed at 20 ml per pot. These were cultivated in a glass greenhouse for 2 days, and then barley powdery mildew spores were collected from the diseased leaves and sprinkled evenly over each plant for inoculation. Next, these were grown in a glass greenhouse for one week, and the degree of barley powdery mildew spots that appeared on each first leaf was investigated. The evaluation of the bactericidal effect was carried out in 6 stages (0: overall diseased,
1: Lesion area is about 60%, 2: Lesion area is about 40%, 3: Lesion area is about 20%, 4: Lesion area is 10%.
Hereinafter, 5: no lesion). Table 25 shows these results.
Shown in

[0177]

[Table 25]

(6) Test for controlling efficacy against wheat rust (preventive effect) Wheat (cultivar: Kobushi wheat) was grown 10 per pot in a plastic flower pot having a diameter of 6 cm. A wettable powder of the compound (I) shown in Tables 2 to 19 prepared according to Example 2 was added to a surfactant (0.01
%) To 500 ppm with water containing
Sprayed at 0 ml. After spraying, cultivation was performed in a glass greenhouse for 2 days, and then a spore suspension of wheat rust (7 × 10
⁴ / ml) was spray-inoculated uniformly on the plant. After inoculation, 1
The plants were grown for a week in a glass greenhouse, and the degree of wheat rust spots on the first leaf was investigated. The results are shown in Table 26 by the six-step evaluation method described in the above (5).

[0179]

[Table 26]

[0180]

The novel aralkylaminopyrimidine derivatives of the present invention are useful pesticides having excellent pest control effects such as excellent insecticidal, acaricidal, nematicidal and fungicidal activities.

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

Claims (3)

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