JPH07258223A - 4-phenethylaminopyrimidine derivative, its production and noxious life controlling agent for agricultural and horticultural use - Google Patents

Abstract

PURPOSE:To provide a new 4-phenethylaminopyrimidlne derivative having excellent insecticidal, miticidal, microbicidal and nematocidal effects and useful as a noxious life controlling agent for agricultural and horticultural use. CONSTITUTION:This compound is expressed by formula I [R<1> is a halogen, OH, an acyloxy, a (halo)alkoxy, an alkylthio, a benzyloxycarbonyloxy, an alkylsulfonyloxy, a trialkylsilyloxy, etc.; R<2> is H, a (halo)alkyl, a halo(alkoxy), a halogen, a (substituted)benzoyl, OH, a haloalkylcarbonyl, an alkylsulfonyloxy, an alkylsulfonyl, an alkylsulfinyl, an alkylthio, a trialkylsilylalkoxy, a (substituted)phenoxy, etc.; (n) is 1-5], e.g. 5-chloro-6-(1-fluoroethyl)-4-(2- phenylethylamino)pyrimidine. The compound can be produced by reacting a pyrimidine derivative of formula II (X is a halogen) with a 4-beta-phenethylamine compound of formula III.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel 4-phenethylaminopyrimidine derivative which is a pesticide for agricultural and horticultural use which is useful as an insecticide, acaricide, fungicide, nematicide and the like. is there.

[0002]

2. Description of the Related Art The following are known as 4-phenethylaminopyrimidine derivatives similar to the present invention. (1) JP-A-57-176967 discloses the following formula

[0003]

[Chemical 4]

[In the formula, R ¹ and R ² represent a lower alkyl group or a halogen atom; X represents an alkylene group; Z is a substituted or unsubstituted phenyl group (the substitution is halogen, lower alkyl and lower alkoxy); 1 or 2 selected from the above), a furyl group or a thienyl group. Note that R ¹ , R ² , X and Z defined by this formula are limited to this formula only. ] It is described that the compound represented by the above is effective as an insecticide, acaricide, and bactericide. (2) Japanese Patent Laid-Open No. 59-36666 discloses the following formula

[0005]

[Chemical 5]

[In the formula, R ¹ and R ² represent a lower alkyl group or a halogen atom, or R ¹ and R ² are condensed to represent a trimethylene group or a tetramethylene group; R ³ is a hydrogen atom or a lower alkyl group. Represents a group; X represents an alkylene group; Z represents a substituted or unsubstituted phenyl group (the substitution is 1 or 2 selected from halogen, lower alkyl and lower alkoxy), a furyl group or a thienyl group. Represents In addition, R ^{1 to} R ³ , X and Z defined by this formula are
Limit to this formula only. ] The compound represented by
It is described as effective as acaricide and fungicide. (3) JP-A-63-225364 discloses the following formula

[0007]

[Chemical 6]

(In the formula, R ¹ represents a hydrogen atom or a lower alkyl group which is unsubstituted or substituted with a halogen atom;
R ² and R ³ each independently represent a halogen atom or a lower alkyl group which is unsubstituted or substituted with a halogen atom, a lower alkoxy group or a lower alkylthio group; R ⁴ is a hydrogen atom, a halogen atom or a lower atom Represents an alkyl group; Q is unsubstituted; or a halogen atom, a nitro group, a lower alkoxy group, a lower alkylthio group, an unsubstituted or a lower alkyl group substituted with a halogen atom or a lower alkoxy group, an unsubstituted, Or a phenyl group substituted with a lower alkoxy group or unsubstituted, or a phenoxy group substituted with a halogen atom or an unsubstituted or lower alkyl group substituted with a halogen atom, a phenyl group or a heterocycle Represents a group; the heterocyclic group may be substituted with an oxo group; A is a cycloalkyl group having 3 to 5 carbon atoms, a lower alkyl group; Represents a lower alkylene group which is substituted with 1 or 2 substituents selected from the group consisting of a nyl group and an unsubstituted or lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkylthio group; B is It represents a direct bond, an oxygen atom, a sulfur atom, a linear or branched lower alkylene group or a lower alkyleneoxy group. In addition, R ^{1 to} R ⁴ defined by this formula,
A, B and Q are limited to this equation only. It is described that the compound represented by () is effective as an insecticide, acaricide, and fungicide. (4) Japanese Patent Application Laid-Open No. 64-68362 discloses the following formula

[0009]

[Chemical 7]

(Wherein R ¹ and R ² independently represent a halogen atom or a lower alkyl group; R ³ represents a lower alkyl group or a cycloalkyl group having 3 to 5 carbon atoms; R ^3
4 represents a halogen atom or a lower alkyl group; n is 0,
1 or 2; Q is an alkyl group having 5 to 10 carbon atoms, an allyl group, a geranyl group, a farnesyl group, a lower alkyl group substituted with 1 to 4 halogen atoms, a cycloalkylmethyl group having 3 to 6 carbon atoms Group, lower alkoxy group, lower alkoxyalkyl group, lower alkylthio group, lower alkylsulfonyl group or ethyl group substituted with phenoxy group substituted with 1 to 2 lower alkyl groups, glycidyl group, acetonyl group, unsubstituted Or a dioxolanylmethyl group substituted with a phenoxymethyl group which may be substituted with a chlorine atom, 2,2-diethoxyethyl group, 1-ethoxycarbonylethyl group, trimethylsilylmethyl group, 1-pyridylethyl group, lower alkoxy A lower amino group substituted with a benzylimino group which may be substituted with an imino group or a lower alkyl group. It represents Kill group. Note that R ^{1 to} R ⁴ , Q and n defined by this formula are limited to this formula. It is described that the compound represented by () is effective as an insecticide, acaricide, and fungicide. (5) Japanese Patent Laid-Open No. 7267/1993 discloses the following formula

[0011]

[Chemical 8]

(Wherein R ¹ is a hydrogen atom, a halogen atom,
Represents a halo lower alkyl group, an alkanoyl group, a nitro group, a cyano group or a 1,3-dioxolan-2-yl group; R
² and R ³ each represent a halogen atom or a lower alkyl group, or R ² and R ³ are fused together with the carbon atom to which they are attached to a pyrimidine ring to have one sulfur atom constituting the ring. Represents a good unsaturated 5- or 6-membered ring; R ⁴ is a hydrogen atom, a halogen atom, a lower alkyl group,
A cycloalkyl group, a lower alkoxy group or an amino group which may be substituted by a lower alkyl group; R ⁵ represents a hydrogen atom, a lower alkyl group or a cycloalkyl group; Z represents a carbon atom or a nitrogen atom. Note that R ^{1 to} R ⁵ and Z defined by this formula are limited to this formula only. It is described that the compound shown by the above) is effective as a fungicide. (6) JP-A-3-163066 discloses the following formula

[0013]

[Chemical 9]

(Wherein R ¹ represents a hydrogen atom or a halogen atom; R ² and R ³ represent a hydrogen atom, a halogen atom or a lower alkyl group, or R ² and R ³ are carbons to which they are condensed. Saturated or unsaturated 5 which may have one sulfur atom which is condensed with the atom to form a pyrimidine ring and constitutes the ring
Or a 6-membered ring; R ⁴ represents a hydrogen atom, a halogen atom, a lower alkyl group, a cycloalkyl group, a lower alkoxy group, a lower alkylthio group or an amino group which may be substituted with lower alkyl; R ⁵ represents hydrogen An atom, a lower alkyl group, a cycloalkyl group or a halo lower alkyl group; R ⁶ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a halo lower alkoxy group;
n represents an integer of 1 or 2. Note that R defined by this formula
^{1 to} R ⁶ and n are limited to this formula only. It is described that the compound shown in () is effective as an insecticide and acaricide. (7) Japanese Patent Application Laid-Open No. 4-225976 discloses the following formula

[0015]

[Chemical 10]

(Wherein R ¹ represents a hydrogen atom, a lower alkyl group or a halogen atom; R ² represents a halogen atom;
R ³ represents a lower alkyl group; or R ² and R ³ are saturated or unsaturated, which may have one sulfur atom fused to the pyrimidine ring together with the carbon atom to which they are attached. Represents a 5- or 6-membered ring; R ⁴ represents a hydrogen atom, a lower alkyl group or a cycloalkyl group; A represents a methylene group or an ethylene group substituted with 1 to 4 halogen atoms. In addition, R ^{1 to} R ⁴ and A defined by this formula are
Limit to this formula only. It is described that the compound shown by the above) is effective as a fungicide. (8) Japanese Patent Laid-Open No. 5-202099 discloses the following formula

[0017]

[Chemical 11]

(In the formula, 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. 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. Note that R ^{1 to} R ³ and n defined by this formula are limited to this formula only. It is described that the compound represented by () is effective as an insecticide, acaricide, fungicide, and nematicide.

However, the disclosure of the 4-β-phenethylaminopyrimidine derivative having a substituent at the 6-position ethyl group of the pyrimidine ring as in the present invention is not recognized. Therefore, since the 4-phenethylaminopyrimidine derivative of the present invention is a novel compound, it also has a useful pesticidal activity for agricultural and horticultural use as an insecticide, acaricide, fungicide, nematicide, etc. unknown.

[0020]

The object of the present invention is to provide a novel 4-
It is intended to provide a phenethylaminopyrimidine derivative, a method for producing the same, and a pesticide for agricultural and horticultural use, which is useful as an insecticide, acaricide, fungicide, nematicide, etc., containing the same as an active ingredient.

[0021]

Means for Solving the Problems As a result of studies to solve the above problems, the present inventors have found that a novel 4-phenethylaminopyrimidine derivative is an insecticide, acaricide, fungicide, nematicide. As a pest control agent for agricultural and horticultural use which is useful as, for example, it has been found to have a remarkable control activity, and the present invention has been completed. That is, the present invention is as follows.
The first invention is represented by the following formula (1):

[0022]

[Chemical 12]

(In the formula, R ¹ is a halogen atom, a hydroxyl group, an acyloxy group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms. 4 alkylthio groups, benzyloxycarbonyloxy group, C2-5 alkyloxycarbonyloxy groups, C1-4 alkylsulfonyloxy groups, tri (C1-4 alkyl) silyloxy groups Or represents an alkyloxycarbonylalkyloxy group having 3 to 6 carbon atoms.

R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom,
C1 to C4 haloalkyl group, C1 to C4 haloalkoxy group, unsubstituted or halogen atom, C1 to C1
4 alkyl groups, C1-4 alkoxy groups, C1-4 haloalkoxy groups or C1-4
Benzoyl group having at least one alkylthio group as a substituent, hydroxyl group, haloalkylcarbonyl group having 2 to 5 carbon atoms, alkylsulfonyloxy group having 1 to 4 carbon atoms, haloalkylsulfonyloxy having 1 to 4 carbon atoms A group, an alkylsulfonyl group having 1 to 4 carbon atoms, an alkylsulfinyl group having 1 to 4 carbon atoms, a haloalkylsulfinyl group having 1 to 4 carbon atoms, a tri (alkyl group having 1 to 4 carbon atoms) silylalkoxy group, Alkylthio group having 1 to 4 carbon atoms, unsubstituted or halogen atom, 1 to 4 carbon atoms
Pyridyloxy group having at least one haloalkyl group as a substituent, unsubstituted or phenoxy group having at least one halogen atom or a haloalkyl group having 1 to 4 carbon atoms as a substituent, alkenyl having 2 to 5 carbon atoms Oxy group, haloalkenyloxy group having 2 to 5 carbon atoms, unsubstituted or benzyl group having at least one halogen atom or hydroxyl group as a substituent, 2-phenyl-
2-1,3-dioxolanyl group, (C1-4 alkoxy) iminobenzyl group, di (C1-4 alkyl) hydrazonobenzyl group, nitro group, C1-C1
It represents 4 haloalkylthio groups or an alkynyloxy group having 2 to 5 carbon atoms. n represents an integer of 1 to 5. *
Represents an asymmetric carbon atom. ) Related to the 4-phenethylaminopyrimidine derivative. The second invention is the following formula (2):

[0025]

[Chemical 13]

(In the formula, R ¹ has the same meaning as above; X represents a halogen atom.) And a pyrimidine derivative represented by the following formula (3):

[0027]

[Chemical 14]

(Wherein R ² and n have the same meanings as defined above), 4-β-phenethylamines represented by the formula 4-are represented by the formula (1).
The present invention relates to a method for producing a phenethylaminopyrimidine derivative. A third aspect of the present invention is the 4-indicated by the above formula (1).
The present invention relates to an agricultural and horticultural pest control agent containing a phenethylaminopyrimidine derivative as an active ingredient.

The present invention will be described in detail below. Target compound and raw material compound A novel 4-phenethylaminopyrimidine derivative [compound (1)] which is a target compound and R ¹ , R ² and n represented by the raw materials [compound (2), compound (3)] ,
It is as follows.

[R ¹ ] R ¹ is a halogen atom, a hydroxyl group, an acyloxy group having 2 to 5 carbon atoms, or 1 to 4 carbon atoms.
Alkoxy groups, C1-4 haloalkoxy groups, C1-4 alkylthio groups, benzyloxycarbonyloxy groups, C2-5 alkyloxycarbonyloxy groups, C1-4 And an alkylsulfonyloxy group, a tri (alkyl having 1 to 4 carbons) silyloxy group, an alkyloxycarbonylalkyloxy group having 3 to 6 carbons, and the like. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; a fluorine atom and a chlorine atom are preferable. Examples of the acyloxy group include those having a linear or branched alkyl group; those having 2 to 4 carbon atoms are preferable;
COCH ₃ is preferred.

The alkoxy group may be a linear or branched one, preferably having 1 to 1 carbon atoms.
It is four or one; more preferably -OCH _3. Examples of the haloalkoxy group include those in which alkoxy is linear or branched and have a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, or a fluorine atom; preferably, it has 1 to 4 carbon atoms. Of that;
More preferably -OCF ₂ CHFCF _3, -OCF ₂
CHFCl. The alkylthio group, there may be mentioned those having a straight-chain or branched alkyl group; and preferably those having 1 to 4 carbon atoms; more preferably -SCH _3. The alkyloxycarbonyl group, but the alkyl group may be mentioned a straight or _{branched; -OCOO-t-C 4 H} 9
Is preferred.

Examples of the alkylsulfonyloxy group include those having a linear or branched alkyl group; -OSO ₂ CH ₃ is preferable. Examples of the trialkylsilyloxy group include those having a linear or branched alkyl group; -OSi
(CH ₃ ) ₃ is preferred. Alkyloxycarbonyl alkyl group, there may be mentioned those having a straight-chain or branched alkyl group; -OCH ₂ C
OOCH ₃ is preferred.

[R ² ] R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms,
C1-C4 haloalkoxy group, benzoyl group, hydroxyl group, C2-C5 haloalkylcarbonyl group, C1-C4 alkylsulfonyloxy group, C1
~ 4 haloalkylsulfonyloxy groups, 1 to 1 carbon atoms
4 alkylsulfonyl groups, 1 to 4 carbon alkylsulfinyl groups, 1 to 4 carbon haloalkylsulfinyl groups, tri (1 to 4 carbon alkyl) silylalkoxy groups, 1 to 4 carbon atoms Alkylthio group, pyridyloxy group, phenoxy group, alkenyloxy group having 2 to 5 carbon atoms, haloalkenyloxy group having 2 to 5 carbon atoms, benzyl group, 2-phenyl-2-1,3-dioxolanyl group, (Alkoxy having 1 to 4 carbons) iminobenzyl group, di (alkyl having 1 to 4 carbons) hydrazonobenzyl group, nitro group, haloalkylthio group having 1 to 4 carbons, 2 to 5 carbons The alkynyloxy group and the like can be mentioned.

The substitution position of R ² is not particularly limited;
The 3-position and the 4-position are preferred. Examples of the alkyl group include linear or branched ones;
Preferably of 1 to 4 carbon atoms; more preferably -CH _3. Examples of the alkoxy group include linear or branched ones; preferably those having 1 to 4 carbon atoms; and more preferably -OCH.
₃ is -OC ₂ H _5. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; a fluorine atom and a chlorine atom are preferable.

Examples of the haloalkyl group include those in which alkyl is linear or branched and have a halogen atom such as a chlorine atom, an iodine atom, a bromine atom or a fluorine atom; —CF ₃ is preferable. As the haloalkoxy group, alkoxy is linear or branched,
Examples thereof include those having a halogen atom such as chlorine atom, iodine atom, bromine atom and fluorine atom;
_{CF 3, -OCHF 2, -OCH 2} CF 3, -OCF 2
_{CHFCF 3, -OCHFCHF 2, -OCF 2} CHF
Cl is preferred.

The benzoyl group is unsubstituted or has a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms or 1 to 4 carbon atoms. Examples thereof include one having an alkylthio group as a substituent. The position of the substituent in the benzoyl group is not particularly limited, but the 4-position is preferable. Examples of the substituted halogen atom of the benzoyl group include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; a fluorine atom and a chlorine atom are preferable. Examples of the substituted alkyl group of the benzoyl group include those having a linear or branched alkyl group;
Preferably of 1 to 4 carbon atoms; more preferably -CH _3.

Examples of the substituted alkoxy group of the benzoyl group include linear or branched ones;
Preferably of 1 to 4 carbon atoms; more preferably -OCH _3. Examples of the substituted haloalkyl group of the benzoyl group include those in which alkyl is linear or branched and have a halogen atom such as a chlorine atom, an iodine atom, a bromine atom or a fluorine atom; To 4; more preferably-
CF _3. The substituted alkylthio group of the benzoyl group, there may be mentioned those having a straight-chain or branched alkyl group; -SCH ₃ are preferred. Examples of the haloalkylcarbonyl group include those in which alkyl is linear or branched and have a halogen atom such as a chlorine atom, an iodine atom, a bromine atom or a fluorine atom; —COCF ₃ is preferable.

Examples of the alkylsulfonyloxy group include those having a linear or branched alkyl group; -OSO ₂ CH ₃ is preferable. Examples of the haloalkylsulfonyloxy group include those in which alkyl is linear or branched and have a halogen atom such as a chlorine atom, an iodine atom, a bromine atom or a fluorine atom; —OSO ₂ CF ₃ is preferable. . The alkylsulfonyl group, there may be mentioned those having a straight-chain or branched alkyl group; -SO ₂ CH ₃ are preferred. The alkylsulfinyl group, there may be mentioned those having a straight-chain or branched alkyl group; -SOCH ₃ are preferred.

Examples of the haloalkylsulfinyloxy group include those in which alkyl is linear or branched and have a halogen atom such as a chlorine atom, an iodine atom, a bromine atom or a fluorine atom; --SOCH ₂ F Is preferred. Examples of the tri (alkyl) silylalkoxy group include linear and branched alkyl and alkoxy groups; preferably alkyl and alkoxy groups having 1 to 4 carbon atoms; and more preferably- OCH ₂ Si (CH ₃ ) ₃ . The alkylthio group, there may be mentioned those having a straight-chain or branched alkyl group; -SCH ₃ are preferred.

As the pyridyloxy group, pyridine-2
Examples include -yl-oxy and pyridin-3-yl-oxy; pyridin-2-yl-oxy is preferable. The pyridyloxy group may have a substituent; examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a haloalkyl group having 1 to 4 carbon atoms. The position of the substituent in the pyridyloxy group is not particularly limited; 3-position and 5-position are preferable. Examples of the substituted halogen atom of the pyridyloxy group include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom, and a chlorine atom is preferable. The substituted haloalkyl group of the pyridyloxy group is a straight-chain or branched alkyl group, a chlorine atom, an iodine atom, a bromine atom,
There may be mentioned those having a halogen atom such as a fluorine atom; -CF ₃ is preferred.

Examples of the phenoxy group include those which are unsubstituted or have a halogen atom or a haloalkyl group having 1 to 4 carbon atoms as a substituent. The position of the substituent on the phenoxy group is not particularly limited. Examples of the substituted halogen atom of the phenoxy group include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom, and a chlorine atom and a fluorine atom are preferable. Examples of the substituted haloalkyl group of the phenoxy group include those in which alkyl is linear or branched and has a halogen atom such as a chlorine atom, an iodine atom, a bromine atom or a fluorine atom, and -CF ₃ is preferable. .

Examples of the alkenyloxy group include linear or branched ones; -OCH ₂ CH
= CH ₂ is preferred. The haloalkenyloxy group is an alkenyl having a straight chain or branched chain, a chlorine atom,
Examples thereof include those having a halogen atom such as an iodine atom, a bromine atom and a fluorine atom; -OCH = CH
_{-CH = CF 2, -OCH 2 CH} 2 CF = CF 2 is preferred. Examples of the benzyl group include those that are unsubstituted or have a halogen atom or a hydroxyl group as a substituent. The position of the substituent in the benzyl group is not particularly limited; however, the α position is preferable. Examples of the substituted halogen atom of the benzyl group include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; a chlorine atom and a fluorine atom are preferable. Examples of the 2-phenyl-2-1,3-dioxolanyl group include those which are unsubstituted or have a halogen atom as a substituent.

The position of the substituent in the 2-phenyl-2-1,3-dioxolanyl group is not particularly limited, but the 4-position of the phenyl moiety is preferred. 2-phenyl-2-1,3
Examples of the substituted halogen atom of the -dioxolanyl group include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; and a chlorine atom is preferable. As the alkoxyiminobenzyl group, linear or branched alkoxy can be mentioned; and -OCH ₃ is preferable. Examples of the dialkylhydrazonobenzyl group include those in which alkyl is linear or branched;
-CH ₃ is preferred. The haloalkylthio group, the alkyl is a linear or branched, a chlorine atom, an iodine atom, a bromine atom, it may be mentioned those having a halogen atom such as a fluorine atom; -SCH ₂ CF ₃ are preferred. Examples of the alkynyloxy group include linear and branched ones; -OCH ₂ C≡CH is preferable. n represents an integer of 1 to 5; 1 or 2 is preferable. * Represents an asymmetric carbon atom.

The compound (1) may be a combination of the above-mentioned various substituents. Preferred compounds from the viewpoint of efficacy are as follows. (1) A compound in which R ¹ is a halogen atom and R ² is a hydrogen atom. (2) A compound in which R ¹ is a hydroxyl group and R ² is a hydrogen atom. (3) R ¹ is an acyloxy group having 2 to 5 carbon atoms, R ^1
A compound in which ² is an alkyl group having 1 to 4 carbon atoms. (4) A compound in which R ¹ is a hydroxyl group and R ² is an alkyl group having 1 to 4 carbon atoms. (5) A compound in which R ¹ is a halogen atom and R ² is an alkyl group having 1 to 4 carbon atoms. (6) A compound in which R ¹ is a halogen atom and R ² is an alkoxy group having 1 to 4 carbon atoms. (7) R ¹ is an acyloxy group having 2 to 5 carbon atoms, R ^1
A compound in which ² is an alkoxy group having 1 to 4 carbon atoms. (8) A compound in which R ¹ is a hydroxyl group and R ² is an alkoxy group having 1 to 4 carbon atoms.

(9) A compound in which R ¹ and R ² are halogen atoms. (10) A compound in which R ¹ is a halogen atom and R ² is a benzoyl group. (11) R ¹ is an acyloxy group having 2 to 5 carbon atoms, R
A compound in which ² is a benzoyl group. (12) A compound in which R ¹ is a hydroxyl group and R ² is a benzoyl group. (13) A compound in which R ¹ is a halogen atom and R ² is a haloalkyl group having 1 to 4 carbon atoms. (14) A compound in which R ¹ is a halogen atom and R ² is a haloalkoxy group having 1 to 4 carbon atoms. (15) R ¹ is an alkylthio group having 1 to 4 carbon atoms, R ¹
A compound in which ² is a benzoyl group. (16) A compound in which R ¹ is a halogen atom and R ² is a haloalkylcarbonyl group having 2 to 5 carbon atoms.

(17) A compound in which R ¹ is an acyloxy group having 2 to 5 carbon atoms and R ² is an alkylsulfonyloxy group having 1 to 4 carbon atoms. (18) A compound in which R ¹ is a hydroxyl group and R ² is an alkylsulfonyloxy group having 1 to 4 carbon atoms. (19) A compound in which R ¹ is a halogen atom and R ² is an alkylsulfonyloxy group having 1 to 4 carbon atoms. (20) R ¹ is an acyloxy group having 2 to 5 carbon atoms, R
^A compound in which ² is a haloalkoxy group having 1 to 4 carbon atoms. (21) A compound in which R ¹ is a hydroxyl group and R ² is a haloalkoxy group having 1 to 4 carbon atoms. (22) R ¹ is an alkoxy group having 1 to 4 carbon atoms, R ²
Wherein C is a haloalkoxy group having 1 to 4 carbon atoms. (23) R ¹ is a benzyloxycarbonyloxy group,
A compound in which R ² is a haloalkoxy group having 1 to 4 carbon atoms. (24) A compound in which R ¹ is an alkyloxycarbonyloxy group having 2 to 5 carbon atoms and R ² is a haloalkoxy group having 1 to 4 carbon atoms. (25) A compound in which R ¹ is a halogen atom and R ² is a haloalkylsulfonyloxy group having 1 to 4 carbon atoms.

(26) A compound in which R ¹ is an acyloxy group having 2 to 5 carbon atoms and R ² is a haloalkylsulfonyloxy group having 1 to 4 carbon atoms. (27) A compound in which R ¹ is an alkylsulfonyloxy group having 1 to 4 carbon atoms and R ² is a benzoyl group. (28) A compound in which R ¹ is a tri (alkyl having 1 to 4 carbons) silyloxy group and R ² is a benzoyl group. (29) R ¹ is an acyloxy group having 2 to 5 carbon atoms, R
^A compound in which ² is a haloalkyl group having 1 to 4 carbon atoms. (30) A compound in which R ¹ is a hydroxyl group and R ² is a haloalkyl group having 1 to 4 carbon atoms. (31) A compound in which R ¹ is a halogen atom and R ² is an alkoxyiminobenzyl group. (32) R ¹ is a halogen atom and R ² is 2-phenyl-
A compound which is a 2-1,3-dioxolanyl group. (33) A compound in which R ¹ is a halogen atom and R ² is a benzyl group.

(34) A compound in which R ¹ and R ² are a haloalkoxy group having 1 to 4 carbon atoms. (35) A compound in which R ¹ is a halogen atom and R ² is a phenoxy group. (36) A compound in which R ¹ is a halogen atom and R ² is a haloalkenyloxy group having 2 to 5 carbon atoms. (37) A compound in which R ¹ is a halogen atom and R ² is an alkenyloxy group having 2 to 5 carbon atoms. (38) R ¹ is a halogen atom, and R ² is tri (1 carbon atom).
To 4 alkyl) silylalkoxy groups. (39) A compound in which R ¹ is a halogen atom and R ² is an alkylthio group having 1 to 4 carbon atoms. (40) A compound in which R ¹ is a halogen atom and R ² is a hydroxyl group. (41) A compound in which R ¹ is a halogen atom and R ² is an alkylsulfonyl group having 1 to 4 carbon atoms.

(42) A compound in which R ¹ is a halogen atom and R ² is an alkylsulfinyl group having 1 to 4 carbon atoms. (43) A compound in which R ¹ is a halogen atom and R ² is a pyridyloxy group. (44) A compound in which R ¹ is a halogen atom and R ² is a haloalkylsulfinyl group having 1 to 4 carbon atoms. (45) A compound in which R ¹ is a halogen atom and R ² is a dialkylhydrazonobenzyl group. (46) A compound in which R ¹ is a hydroxyl group and R ² is a benzyl group. (47) A compound in which R ¹ is a halogen atom and R ² is a nitro group.

Consisting of these preferred combinations (1)
As R ¹ and R ² of the compound (1) represented by
The above-mentioned preferable ones and more preferable ones can be exemplified. Specific examples of these compounds (1) include:
Compounds 1 to 16 and 18 described in Tables 2 to 17 below
29, 33, 34, 38-56, 58-93, 108-
114 can be mentioned.

Since the compound (1) of the present invention has an amino group, acid addition salts derived from them are also included in the present invention. Examples of acids forming acid addition salts include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid; formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, aconitic acid, etc. Carboxylic acids; organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid; and saccharin. In addition, since the compound (1) of the present invention contains an asymmetric carbon atom represented by *, the individual optical isomers derived from these,
Either racemates or mixtures thereof are included in the invention.

Method of Synthesizing Compound (1) As a preferred embodiment for producing the 4-phenethylaminopyrimidine derivative represented by the above-mentioned formula (1),
In addition to the synthesis method 1 described as the invention of, the following five production methods (synthesis methods 2 to 6) can be mentioned. (Synthesis Method 2) The following formula (1-1):

[0053]

[Chemical 15]

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

[0055]

[Chemical 16]

(In the formula, R ⁴ represents a lower acyloxy group.) In the above formula (1), R ¹ is a lower acyloxy group, which is characterized by reacting with a lower aliphatic carboxylic acid. 4-phenethylaminopyrimidine derivative [referred to as compound (1-2). ] Manufacturing method. (Synthesis Method 3) The following formula (1-2):

[0057]

[Chemical 17]

(Wherein R ² , n, * and R ⁴ have the same meanings as described above) and a 4-phenethylaminopyrimidine derivative represented by the following formula (5):

[0059]

[Chemical 18]

A 4-phenethylaminopyrimidine derivative represented by the above formula (1), wherein R ¹ is a hydroxyl group, characterized by reacting with an inorganic base represented by the formula (M represents an alkali metal). [Referred to as compound (1-3). ] Manufacturing method. (Synthesis Method 4) A 4-phenethylaminopyrimidine derivative represented by the above formula (1-1) and the following formula (6):

[0061]

[Chemical 19]

(In the formula, R ⁵ represents a lower alkyl group; Y
Represents an oxygen atom or a sulfur atom. And an alcohol (or a mercaptan) represented by the formula (4), wherein R ¹ is a lower alkoxy group (or a lower alkylthio group) in the above formula (1). It is called (1-4). ] Manufacturing method. (Synthesis Method 5) A 4-phenethylaminopyrimidine derivative represented by the above formula (1-1) and the following formula (7):

[0063]

[Chemical 20]

(In the formula, M has the same meaning as defined above), the alkali metal fluorine compound represented by the formula (1) is reacted with R ¹ to represent a fluorine atom. Phenethylaminopyrimidine derivative [referred to as compound (1-5). ] Manufacturing method. (Synthesis Method 6) The following formula (1-3):

[0065]

[Chemical 21]

(Wherein R ² , n and * have the same meanings as defined above) and a 4-phenethylaminopyrimidine derivative represented by the following formula (8):

[0067]

[Chemical formula 22]

A process for producing the compound (1-5), which comprises reacting with a fluorinating agent represented by: The synthetic methods 1 to 6 of the compound (1) of the present invention will be described in more detail. [Synthesis Method 1] The synthesis method 1 comprises the compound (2) and the compound (3).
Is a method of reacting with and in a solvent to obtain a compound (1), and the reaction can be promoted by reacting in the presence of a base.

The type of solvent is not particularly limited as long as it does not directly participate in this reaction, and for example, benzene,
Chlorinated and unchlorinated aromatics, aliphatics, fats such as toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane Cyclic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; ketones such as acetone, methyl ethyl ketone, etc .; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, etc .; Nitriles such as acetonitrile, propionitrile, etc .; triethylamine, pyridine, N,
Organic bases such as N-dimethylaniline; 1,3-
Dimethyl-2-imidazolidone; dimethylsulfoxide; mixtures of the solvents mentioned.

The amount of the solvent used is 5 to 80 for the compound (2).
It can be used by making it to be a weight%; 10
˜70 wt% is preferred. The type of base is not particularly limited, and examples thereof include triethylamine, pyridine, N,
Organic bases such as N-dimethylaniline, DBU, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, etc. Mention may be made of inorganic bases; organic bases are preferred.

The amount of the base used is 0.001 to 5 times by mole with respect to the compound (2); preferably 0.8 to 2 times by mole. The reaction temperature is not particularly limited, but is within a temperature range of room temperature to the boiling point of the solvent used; 80 to 11
0 ° C is preferred. The reaction time varies depending on the above-mentioned concentration and temperature; it is usually 0.3 to 4 hours. The amount of the raw material compound used was 0.
It is 5 to 2 times mol; but 1.0 to 1.2 times mol is preferable. Compound (2) used in the present invention (when R ¹ = X)
Similarly to the method described in JP-A-5-194417, the compound (9-1) and the compound (10-
It can be produced by reacting 1) with a solvent.

[0072]

[Chemical formula 23]

(In the formula, in the case of R ¹ = X, X has the same meaning as described above.) Examples of the solvent include the above-mentioned ones; It can be used in an amount of up to 80% by weight. The reaction temperature is not particularly limited, but is 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; it is usually 2 to 10 hours. The amount of the raw material compound used is 0.5 to 3 times mol of the compound (10-1) with respect to the compound (9-1); preferably 0.5 to 1.7 times mol. The compound (9-1) can be obtained, for example, from Journal of Chemical Society (JCS) 3478 to 3481 (195).
According to the method described in 5 years), it can be produced by carrying out as shown in the following formula.

[0074]

[Chemical formula 24]

(In the formula, X has the same meaning as above.) The compound (2) produced as described above may be subjected to usual post-treatments such as extraction, concentration and filtration after the reaction, Accordingly, it can be appropriately purified by a known means such as recrystallization or various chromatography. Examples of the compound (2) include compounds (2-1) to (2-7) shown in Table 1 below. The compound (3) used in the present invention is
It can be manufactured by carrying out as shown in the following formula.

[0076]

[Chemical 25]

(In the formula, R ² and n have the same meanings as described above.) The compound (3) is composed of the kinds of the respective substituents corresponding to the compounds 1 to 114 shown in Tables 2 to 17 below. Compound (3) [Compounds (3) ₁ to (3) ₁₁₄ are referred to as. For example, in the compound (3) ₁ , R ^{2 in the} formula represented by the compound (3) is a hydrogen atom and n is 1. ] Etc. can be mentioned. Examples of the target compound (1) synthesized as described above include compounds 1-114 shown in Tables 2 to 17 below (for example, compound 1 is represented by compound (1)). In the formula, R ¹ is a fluorine atom, R ² is a hydrogen atom, and n is 1. ].

[Synthesis Method 2] In Synthesis Method 2, a compound (1-1) and a compound (4) are reacted in a solvent or in the absence of a solvent.
(1-2) A method of obtaining [a compound in which R ¹ in compound (1) is a lower acyloxy group], and the reaction can be promoted by reacting in the presence of a base.
Examples of the solvent include, in addition to the solvent described in Synthesis Method 1, aliphatic carboxylic acids such as acetic acid and propionic acid, mixtures thereof, and the like; N, N-dimethylformamide and introduction. The same aliphatic carboxylic acid as the acyloxy group is preferred. The amount of the solvent used is the compound (I
-1) can be used in an amount of 5 to 80% by weight; preferably 10 to 70% by weight. Examples of the type of base include the bases described in Synthesis Method 1; inorganic bases are preferred.

The amount of base used is 1 with respect to compound (1-1).
˜5 times mole; preferably 2 to 5 times mole. The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent used; 80 to 120 ° C. is preferable. The reaction time varies depending on the above-mentioned concentration and temperature; it is usually 2 to 10 hours. As the compound (4), a commercially available product can be used. The desired compound (1-2) 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 recrystallization, various chromatographic methods, etc. It can be appropriately purified by means. The compound (1-2) is shown in Tables 2 to 1 below.
Compounds 4, 8, 12, 19, 23, 27 shown in 7
36, 45, 49, 56, 63, 66, 109, 113
And so on.

[Synthesis Method 3] In Synthesis Method 3, compound (1-2) and compound (5) are reacted in a solvent to give compound (1-3) [R ¹ in compound (1) is a hydroxyl group. Compound], and the reaction can be promoted by reacting in the presence of a base. Examples of the solvent include, in addition to the ethers, ketones, and amides described in Synthesis Method 1, alcohols (methanol, ethanol, propanol, butanol, etc.), water, and a mixture of the solvents. A mixture of alcohols and water is preferred. The amount of the solvent used can be such that the compound (1-2) is 5 to 80% by weight;
0% by weight is preferred. 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 is 1 to 5 times mol, preferably 2 to 5 times mol, of the compound (1-2).

The reaction temperature is not particularly limited, but is within the temperature range from room temperature to the boiling point of the solvent used; room temperature to
50 ° C is preferred. The reaction time varies depending on the above concentration and temperature; it is usually 0.5 to 1 hour. As the compound (5), a commercially available product can be used. The target compound (1-3) produced as described above is
It may be subjected to usual post-treatments such as extraction, concentration and filtration, and if necessary, it may be appropriately purified by a known means such as recrystallization and various chromatographies. As compound (1-3),
Compounds 2, 5, 9, 13, shown in Tables 2 to 17 below,
20, 24, 28, 37, 46, 50, 57, 64, 6
7,92,110,114 etc. can be mentioned.

[Synthesis Method 4] In Synthesis Method 4, a compound (1-1) and a compound (6) are reacted in a solvent or in the absence of a solvent.
(1-4) a method of obtaining [a compound (1) in which R ¹ is an alkoxy group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms], and reacting in the presence of a base By doing so, the reaction can be promoted. Examples of the solvent include ethers, ketones, amides and a mixture of the above-mentioned solvents described in Synthesis Method 1; ketones and amides are preferable. The solvent may be used in an amount of 5 to 80% by weight of compound (1-1); preferably 10 to 70% by weight.
Examples of the type of base include the bases described in Synthesis Method 1; inorganic bases are preferred. The amount of base used is
It is a 1- to 5-fold molar quantity versus the compound (1-1); preferably a 1- to 3-fold molar quantity.

The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent used; room temperature to
60 ° C is preferred. The reaction time varies depending on the above-mentioned concentration and temperature, but is usually 0.3 to 2 hours. As the compound (6), a commercially available product can be used. The target compound (1-4) produced as described above, after the reaction is completed,
It may be subjected to usual post-treatments such as extraction, concentration and filtration, and if necessary, it may be appropriately purified by a known means such as recrystallization and various chromatographies. As compound (1-4),
Compounds 39, 40, 52 shown in Tables 2 to 17 below,
89 etc. can be mentioned.

[Synthesis Method 5] In Synthesis Method 5, compound (1-1) and compound (7) are reacted in a solvent to give compound (1-5) [wherein R ¹ in compound (1) is a fluorine atom. A certain compound], and the reaction can be promoted by heating and reacting. As the type of solvent, N,
Examples thereof include amides such as N-dimethylformamide and N, N-dimethylacetamide; 1,3-dimethyl-2-imidazolidone; dimethylsulfoxide; sulfolane; and mixtures of the above solvents. The solvent may be used in an amount of 5 to 80% by weight of compound (1-1); preferably 10 to 70% by weight.
Examples of the compound (7) include alkali metal fluorine compounds; cesium fluoride, potassium fluoride and the like are preferable. The proportion of solvent used is compound (1-
The amount is 1 to 5 times, but preferably 1.2 to 3 times the mol of 1). The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent used; 100
~ 140 ° C is preferred. The reaction time varies depending on the above-mentioned concentration and temperature; it can usually be carried out for 1 to 8 hours.

[Synthesis Method 6] In addition to Synthesis Method 5, the compound (1-5) can be synthesized by reacting the compound (1-3) with a fluorinating agent in a solvent. Synthetic method 6 is a method of reacting compound (1-3) with a fluorinating agent in a solvent to give a compound
This is a method of obtaining (1-5). As the solvent, chlorinated or non-chlorinated aromatic, aliphatic or alicyclic hydrocarbons described in Synthesis Method 1; ethers such as diethyl ether, tetrahydrofuran, dioxane; mixtures of the above solvents, etc. Can be mentioned. The solvent may be used in an amount of 5 to 80% by weight of compound (1-3); preferably 10 to 70% by weight. The fluorinating agent is not particularly limited, but the following formula:

[0086]

[Chemical formula 26]

For example, diethylaminosulfur trifluoride (DAST) represented by can be used. The amount used is 1- to 5-fold molar amount with respect to compound (1-3); preferably 1-2-fold molar amount with respect to compound (1-1).
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; the ice cooling temperature to room temperature is preferable. The reaction time varies depending on the above concentration and temperature, but is usually 0.3 to 2 hours. The target compound (1-5) produced by the synthetic methods 5 and 6 is subjected to usual post-treatments such as extraction, concentration and filtration after the completion of the reaction, and if necessary, known methods such as recrystallization and various chromatographies. It can be appropriately purified by the above method. Examples of the compound (I-5) include compounds 1, 6, 10 shown in Tables 2 to 17 below.
14, 15, 17, 21, 21, 25-29 to 34, 38, 4
3,47,51,58,68-71,73-75,77
~ 88,93-107,111 etc. can be mentioned.

Pest control agent for agricultural and horticultural use [controlling effect] As a pest in agricultural and horticultural activities that is recognized to have a controlling effect by the compound (1) of the present invention, there are agricultural and horticultural pests [eg, Hemiptera (Pondidae, leafhopper). Aphids,
Whiteflies, etc.), Lepidoptera (Beetle beetles, diamondback moth,
Leaf beetles, leaf moths, hornworms, butterflies, etc.), Coleoptera (Galloridae, Weevil),
Chrysomelidae, chafers, etc.), mites (such as citrus mites of the mite family, citrus spider mites of the mite family, etc.)], hygiene pests (eg, flies, mosquitoes, cockroaches), stored-product pests (Scots beetles, weevil) ), Root-knot nematodes in the soil, pine wood nematodes, mite, etc., and agricultural and horticultural pathogens (eg, wheat red rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato blight). Can be mentioned.

[Pest Control Agent] The pest control agent for agricultural and horticultural use of the present invention is particularly prominent in insecticidal, acaricidal, bactericidal and nematicidal effects, and one or more compounds (1) are effective. It is contained as an ingredient. The compound (1) can be used alone, but is usually mixed with a carrier, a surfactant, a dispersant, an auxiliary agent and the like by a conventional method (eg, powder, emulsion, fine granule, granule, hydrate). It is preferably prepared as a composition such as an agent, an oily suspension, or an aerosol).

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

Surfactants and dispersants that can be used to improve the performance of the present agent such as adhesion to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading and the like include, for example, alcohol sulfates and alkyls. Examples thereof include sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like. In order to improve the properties of the preparation, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic or the like can be used as an auxiliary agent. In the production of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in appropriate combination according to the purpose. The concentration of the active ingredient when the compound (I) of the present invention is formulated is usually 1 to 50% by weight for emulsions, 0.3 to 25% by weight for powders, and usually 1 to 90% for wettable powders.
% By weight, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils, and usually 0.1 to 5% by weight for aerosols. These formulations can be diluted to an appropriate concentration and sprayed on the surface of plant foliage, soil, water surface of paddy fields or directly applied to various applications depending on the purpose.

[0092]

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 Compound (2)] (1) Synthesis of 6- (1-chloroethyl) -4,5-dichloropyrimidine [Compound (2-1)] 4,5-Dichloro-6-ethylpyrimidine (270 g )
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 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 a target product which was a pale yellow liquid.

(2) Synthesis of 4,5-dichloro-6- (1-fluoroethyl) pyrimidine [Compound (2-4)] 6- (1-hydroxyethyl) -4,5-dichloropyrimidine (2.1 g) Was dissolved in dichloromethane (15 ml), diethylaminosulfur trifluoride (2.0 g) was added dropwise with 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 (Wakogel C-200, eluted with chloroform) to obtain 1.3 g of the target product as a pale yellow oily liquid.

B. p. 229-231 ° C ¹ H-NMR (CDCl ₃ , δppm) 1.64-1.81 (3H, d-d), 5.84-6.
19 (1H, dq), 8.92 (1H, s)

(3) 5-chloro-4-fluoro-6- (1
-Fluoroethyl) pyrimidine [Compound (2-5)] Synthesis of 4,5-dichloro-6- (1-fluoroethyl) pyrimidine (1.3 g) was performed using 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.

B. p. 192-194 ° C ¹ H-NMR (CDCl ₃ , δppm) 1.66-1.82 (3H, d-d), 5.85-6.
21 (1H, dq), 8.83 (1H, s)

(4) 6- (1-acetoxyethyl) -4,
Synthesis of 5-dichloropyrimidine [Compound (2-6)] 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, and 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 (Wako Gel C-20
0, toluene: ethyl acetate = 10: 1 elution) to obtain 5.2 g of the desired product as a pale yellow liquid.

¹ H-NMR (CDCl ₃ , δppm) 1.55 to 1.62 (3H, d), 2.15 (3H,
s), 6.00 to 6.12 (1H, q), 8.84 (1
H, s)

(5) Synthesis of 4,5-dichloro-6- (1-hydroxyethyl) pyrimidine [Compound (2-7)] 6- (1-acetoxyethyl) -4,5-dichloropyrimidine (4.0 g) ) To tetrahydrofuran (50 ml)
And 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.

¹ H-NMR (CDCl ₃ , δppm) 1.47 to 1.52 (3H, d), 3.76 to 3.85
(1H, d), 5.17 to 5.25 (1H, m), 8.
88 (1H, s) (6) Synthesis of other raw material compounds (2) in Table 1 Other raw material compounds (2) in Table 1 were synthesized in the same manner as in (1) to (5) above. .

[0101]

[Table 1]

Example 1 [Synthesis of Compound (1)] The target compound (1) was synthesized using the compound (2) obtained in Reference Example 1. (1) 5-chloro-6- (1-fluoroethyl) -4-
(2-Phenylethylamino) pyrimidine [Compound 1]
Synthesis of 2-phenylethylamine (1.2 g) and triethylamine (1.2 g) were dissolved in toluene (30 ml),
4,5-Dichloro-6- (1-fluoroethyl) pyrimidine (2.0 g) was added, and the mixture was heated under reflux for 4 hours. After completion of the reaction, water was added to the reaction mixture, the target compound was extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was applied to a silica gel column (Wakogel C-200, toluene: ethyl acetate =
Purification by elution (10: 1) gave 2.3 g of the target compound as colorless powdery crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.59 to 1.72 (3H, d-d), 2.84 to 2.
95 (2H, t), 3.71 to 3.79 (2H, q),
5.48-5.60 (1H, m), 5.73-6.01
(1H, m), 7.11 to 7.36 (5H, m), 8.
52 (1H, s)

(2) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- (2-phenylethylamino) pyrimidine [Compound 2] 2-phenylethylamine (1.2 g) and triethylamine (1.2 g) ) And are dissolved in toluene (30 ml),
4,5-Dichloro-6- (1-hydroxyethyl) pyrimidine (2.0 g) was added and the mixture was heated under reflux for 3 hours. After completion of the reaction, water was added to the reaction mixture, the target compound was extracted with toluene, 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 a silica gel column (Wakogel C-200, toluene: ethyl acetate = 5: 1 elution) to obtain 2.2 g of the target compound as colorless powdery crystals.

(3) Synthesis of 5-chloro-6- (1-chloroethyl) -4- [2- (4-methylphenyl) ethylamino] pyrimidine [Compound 3] 2- (4-methylphenyl) ethylamine (4 .1g)
And triethylamine (5.0 g) with toluene (100
ml), 4,5-dichloro-6- (1-chloroethyl) pyrimidine (6.3 g) was added, and the mixture was heated under reflux for 3 hours. After completion of the reaction, water was added to the reaction mixture, the target compound was extracted with toluene, 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 a silica gel column (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 8.4 g of the target compound as colorless powdery crystals.

(4) 6- (1-acetoxyethyl) -5-
Synthesis of Chloro-4- [2- (4-methylphenyl) ethylamino] pyrimidine [Compound 4] Compound 3 (3.5 g) obtained in (3) above was dissolved in N, N-dimethylformamide (50 ml). , Potassium acetate (1.4 g) and potassium carbonate (1.6 g) were added, and the mixture was stirred at about 60 ° C. for 4 hours. After completion of the reaction, water was added to the reaction mixture, 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 resulting oily substance was applied to a silica gel column (Wako Gel C
-200, toluene: ethyl acetate = 4: 1 elution) to obtain 2.0 g of the target compound as a colorless oily liquid.

(5) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- [2- (4-methylphenyl) ethylamino] pyrimidine [Compound 5] The compound 4 (obtained in the above (4) ( 2.3 g of ethanol (2
5 ml) and 1N-sodium hydroxide aqueous solution (1
3 ml) was added, and the mixture was heated with stirring at about 60 ° C. for 1 hour. After completion of the reaction, water was added to the reaction mixture, 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 oily substance thus obtained was purified by a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 4: 1) to obtain 2.0 g of a target compound as a colorless oily liquid.

(6) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- [2- (4-methylphenyl) ethylamino] pyrimidine [Compound 6] The compound 5 (obtained in the above (5) 1.5 g) was dissolved in methylene chloride (30 ml), diethylaminosulfur trifluoride (DAST) (0.8 g) was added dropwise under stirring with ice cooling, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, water was slowly added to the reaction mixture under ice-cooling stirring, the organic solvent layer was separated, the organic solvent layer was washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was subjected to silica gel column chromatography (Wako Gel C
-200, toluene: ethyl acetate = 10: 1 elution) to obtain 1.0 g of the target compound as a pale yellow oily liquid.

(7) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- [2- (4-methoxyphenyl) ethylamino] pyrimidine [Compound 10] 5-chloro-6- (1-chloroethyl ) -4- [2-
(4-Methoxyphenyl) ethylamino] pyrimidine (1.5 g) was added to N, N-dimethylformamide (30 m
It melt | dissolved in 1), cesium fluoride (1.5g) was added, and it stirred at 120-140 degreeC for 12 hours. After completion of the reaction, water was added to the reaction mixture, 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 applied to a silica gel column (Wakogel C-200, toluene: ethyl acetate =
Purification (9: 1 elution) gave 0.5 g of the target compound as colorless powdery crystals.

(8) 5-chloro-4- {2- [4- (4-
Chlorobenzoyl) phenyl] ethylamino} -6-
Synthesis of (1-fluoroethyl) pyrimidine [Compound 25] 5-chloro-4- {2- [4- (4-chlorobenzoyl) phenyl] ethylamino} -6- (1-hydroxyethyl) pyrimidine (0.8 g ) To methylene chloride (20
ml), DAST (0.4 g) was added dropwise under stirring with ice cooling, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, water was slowly added to the reaction mixture with stirring under ice-cooling, the organic solvent layer was separated, the organic solvent layer was 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 a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 10: 1) to obtain 0.4 g of the target compound as a colorless oily liquid.

¹ H-NMR (CDCl ₃ , δppm) 1.57 to 1.72 (3H, dd), 3.02 to 3.
07 (2H, t), 3.79 to 3.89 (2H, m),
5.51 to 5.65 (1H, m), 5.76 to 6.01
(1H, dq), 7.31 to 7.39 (2H, d),
7.43-7.49 (2H, d), 7.72-7.77
(4H, m), 8.56 (1H, s)

(9) Synthesis of 5-chloro-6- (1-chloroethyl) -4- {2- [4- (4-methylbenzoyl) phenyl] ethylamino} pyrimidine [Compound 26] 2- [4- ( 4-Methylbenzoyl) phenyl] ethylamine (4.0 g) and triethylamine (7.0 g) were dissolved in toluene (20 ml), and 4,5-dichloro-
6- (1-Chloroethyl) pyrimidine (4.0 g) was added, and the mixture was stirred at 60 ° C for 3 hr. After completion of the reaction, water was added to the reaction mixture, the target compound was extracted with toluene, washed with water,
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oily substance was purified by a silica gel column (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 2.0 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.82 to 1.85 (3H, d), 2.45 (3H,
s), 2.99 to 3.08 (2H, t), 3.80 to
3.88 (2H, m), 5.36 to 5.43 (1H,
q), 5.56 to 5.68 (1H, m), 7.28 to
7.38 (4H, d-d), 7.69 to 7.80 (4
H, dd), 8.57 (1H, s)

(10) 6- (1-acetoxyethyl) -5-
Synthesis of Chloro-4- {2- [4- (4-methylbenzoyl) phenyl] ethylamino} pyrimidine [Compound 27] Compound 26 (1.5 g) obtained in (9) above was converted to N, N-dimethylformamide ( 30 ml), potassium acetate (0.7 g) was added, and the mixture was stirred at about 60 ° C. for 4 hr. After completion of the reaction, water was added to the reaction mixture, 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 a silica gel column (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 1.3 g of the target compound as a colorless oily liquid.

¹ H-NMR (CDCl ₃ , δppm) 1.53 to 1.55 (3H, d), 2.13 (3H,
s), 2.44 (3H, s), 3.00 to 3.05 (2
H, t), 3.79 to 3.84 (2H, m), 5.54.
Up to 5.56 (1H, m), 5.97 to 6.04 (1H,
q), 7.27 to 7.36 (4H, d-d), 7.69
~ 7.78 (4H, dd), 8.52 (1H, s)

(11) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- {2- [4- (4-methylbenzoyl) phenyl] ethylamino} pyrimidine [Compound 28] In the above (10) The obtained compound 27 (1.0 g) was dissolved in N, N-dimethylformamide (50 ml), 1N-aqueous sodium hydroxide solution (20 ml) was added, and the mixture was stirred at about 60 ° C. for 1 hr. After completion of the reaction, water was added to the reaction mixture, 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 a silica gel column (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 0.7 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.41 to 1.43 (3H, d), 2.44 (3H,
s), 2.95 to 3.06 (2H, t), 3.80 to
3.89 (2H, m), 4.16 to 4.19 (1H,
m), 4.96 to 5.02 (1H, m), 5.53 to
5.59 (1H, m), 7.27 to 7.35 (4H, d
-D), 7.69 to 7.77 (4H, d-d), 8.5
0 (1H, s)

(12) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- {2- [4- (4-methylbenzoyl) phenyl] ethylamino} pyrimidine [Compound 29] In the above (11), The obtained compound 28 (0.38 g) was dissolved in methylene chloride (20 ml), and DAST (0.
18 g) was added dropwise and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the mixture was stirred under ice-cooling, water was slowly added to the reaction mixture, the organic solvent layer was separated, the organic solvent layer was washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oily substance was applied to a silica gel column (Wako Gel C-20
0, toluene: ethyl acetate = 10: 1 elution) to obtain 0.2 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.61-1.72 (3H, d-d), 2.44 (3
H, s), 3.01 to 3.06 (2H, t), 3.81
~ 3.89 (2H, m), 5.57-5.64 (1H,
m), 5.76 to 6.01 (1H, dq), 7.27
~ 7.35 (4H, d-d), 7.69-7.78 (4
H, dd), 8.56 (1H, s)

(13) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- {2- [4- (trifluoromethyl) phenyl] ethylamino} pyrimidine [Compound 33] 2- [4- ( Trifluoromethyl) phenyl] ethylamine (1.9 g) and triethylamine (3.0 g) were dissolved in toluene (20 ml) to give 4,5-dichloro-6.
-(1-Fluoroethyl) pyrimidine (2.0 g) was added, and the mixture was stirred at about 60 ° C for 4 hr. After completion of the reaction, water was added to the reaction mixture, the target compound was extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue is a silica gel column (Wako gel C-200, toluene: ethyl acetate = 10: 1 elution).
2.7 g of the target compound, which is colorless crystals, was obtained by purification by.

¹ H-NMR (CDCl ₃ , δppm) 1.60 to 1.72 (3H, d-d), 2.99 to 3.
04 (2H, t), 3.78 to 3.86 (2H, m),
5.48-5.62 (1H, m), 5.76-6.01
(1H, dq), 7.33 to 7.36 (2H, d),
7.57 to 7.60 (2H, d), 8.56 (1H,
s)

(14) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- {2- [4- (trifluoromethoxy) phenyl] ethylamino} pyrimidine [compound 34] 2- [4- ( Trifluoromethoxy) phenyl] ethylamine (2.05 g) and triethylamine (3.0 g)
And were dissolved in toluene (20 ml), and 4,5-dichloro-6- (1-fluoroethyl) pyrimidine (2.0 g)
Was added and stirred at about 60 ° C. for 4 hours. After completion of the reaction, water was added to the reaction mixture, the target compound was extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by a silica gel column (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 2.6 g of a target compound as pale yellow crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.62-1.73 (3H, d-d), 2.92-3.
01 (2H, t), 3.76 to 3.85 (2H, m),
5.46-5.62 (1H, m), 5.78-6.04
(1H, dq), 7.11 to 7.20 (2H, d),
7.22 to 7.28 (2H, d), 8.59 (1H,
s)

(15) Synthesis of 5-chloro-6- (1-chloroethyl) -4- {2- [4- (2,2,2-trifluoroethoxy) phenyl] ethylamino} pyrimidine [Compound 48] 2 -[4- (2,2,2-trifluoroethoxy) phenyl] ethylamine (5.5 g) and triethylamine (6.0 g) were dissolved in toluene (100 ml),
4,5-Dichloro-6- (1-chloroethyl) pyrimidine (6.4 g) was added, and the mixture was stirred at about 60 ° C for 4 hr. After completion of the reaction, water was added to the reaction mixture, the target compound was extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 7.5 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.82 to 1.91 (3H, d), 2.88 to 2.93
(2H, t), 3.72 to 3.80 (2H, m), 4.
30 to 4.39 (2H, q), 5.36 to 5.43 (1
H, q), 5.55 to 5.60 (1H, m), 6.89
Up to 6.93 (2H, d), 7.16 to 7.26 (2H,
d), 8.54 (1H, s)

(16) 6- (1-acetoxyethyl) -5-
Chloro-4- {2- [4- (2,2,2-trifluoroethoxy) phenyl] ethylamino} pyrimidine [Compound 49] Synthesis of Compound 48 (3.8 g) obtained in (15) above in N, It was dissolved in N-dimethylformamide (30 ml), potassium acetate (1.9 g) and potassium carbonate (2.6 g) were added, and the mixture was stirred at about 60 ° C. for 4 hr. After completion of the reaction, water was added to the reaction mixture, 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 residue is purified by a silica gel column (Wako Gel C-
200, toluene: ethyl acetate = 10: 1 elution) to obtain 3.8 g of the target compound as a colorless oily liquid.

¹ H-NMR (CDCl ₃ , δppm) 1.52 to 1.55 (3H, d), 2.13 (3H,
s), 2.86 to 2.91 (2H, t), 3.72 to
3.75 (2H, m), 4.29-4.39 (2H,
q), 5.45 to 5.55 (1H, m), 5.96 to
6.01 (1H, q), 6.89 to 6.92 (2H,
d), 7.16 to 7.19 (2H, d), 8.49 (1
H, s)

(17) Synthesis of 5-chloro-6- (1-hydroxyethyl) -4- {2- [4- (2,2,2-trifluoroethoxy) phenyl] ethylamino} pyrimidine [Compound 50] The compound 49 (3.6 g) obtained in (16) above was dissolved in ethanol (40 ml), 1N-aqueous sodium hydroxide solution (20 ml) was added, and the mixture was stirred at about 60 ° C. for 1 hr. After completion of the reaction, water was added to the reaction mixture, 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 residue was purified by a silica gel column (Wakogel C-200, toluene: ethyl acetate = 4: 1 elution) to obtain 3.1 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.40 to 1.43 (3H, d), 2.88 to 2.93
(2H, t), 3.72 to 3.83 (2H, m), 4.
13 to 4.16 (1H, m), 4.29 to 4.39 (2
H, q), 4.95 to 5.01 (1H, m), 5.42
Up to 5.55 (1H, m), 6.89 to 6.94 (2H,
d), 7.16 to 7.19 (2H, d), 8.48 (1
H, s)

(18) Synthesis of 5-chloro-6- (1-fluoroethyl) -4- {2- [4- (2,2,2-trifluoroethoxy) phenyl] ethylamino} pyrimidine [Compound 51] The compound 50 (2.8 g) obtained in the above (17) was dissolved in methylene chloride (30 ml), and the mixture was stirred under ice cooling and the DAST (1.4 g) was obtained.
g) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, water was slowly added to the reaction mixture with stirring under ice-cooling, the organic solvent layer was separated, the organic solvent layer was washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was subjected to silica gel column chromatography (Wako gel C-200, toluene: ethyl acetate = 10: 1 elution).
2.2 g of the target compound which is colorless crystals were obtained by purification.

¹ H-NMR (CDCl ₃ , δppm) 1.60 to 1.75 (3H, d-d), 2.88 to 2.
93 (2H, t), 3.72 to 3.83 (2H, m),
4.30-4.39 (2H, q), 5.44-5.60
(1H, m), 5.75 to 6.00 (1H, dq),
6.88-6.92 (2H, d), 7.15-7.19
(2H, d), 8.55 (1H, s)

(19) 5-chloro-6- (1-methylthio)
Synthesis of 4--4- {2- [4- (4-methylthiobenzoyl) phenyl] ethylamino} pyrimidine [Compound 89] 5-chloro-6- (1-chloroethyl) -4- {2-
[4- (4-Methylthiobenzoyl) phenyl] ethylamino} pyrimidine (1.3 g) was dissolved in tetrahydrofuran (20 ml), and 15% methyl mercaptan Na was dissolved.
An aqueous salt solution (1.4 g) was added and the reaction was completed by stirring at about 60 ° C. for 2 hours. After completion of the reaction, water was added to the reaction mixture, 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 residue is purified by a silica gel column (Wako Gel C-20
0, toluene: ethyl acetate = 10: 1 elution) to obtain 1.1 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.59 to 1.62 (3H, d), 2.60 (3H,
s), 2.53 (3H, s), 3.00 to 3.06 (2
H, t), 3.79 to 3.86 (2H, m), 4.28.
Up to 4.36 (1H, q), 5.51 to 5.60 (1H,
m), 7.27 to 7.35 (4H, m), 7.72 to
7.74 (2H, d), 7.75 to 7.76 (2H,
d), 8.52 (1H, s)

(20) 5-chloro-6- (1-fluoroethyl) -4- {2- [4- (2,2,2-trifluoroethoxy) -3-methylphenyl] ethylamino} pyrimidine [compound 93] Synthesis of 2- [4- (2,2,2-trifluoroethoxy) -3
-Methylphenyl] ethylamine (2.3 g) and triethylamine (3.0 g) were dissolved in toluene (40 ml) to give 4,5-dichloro-6- (1-fluoroethyl).
Pyrimidine (2.0 g) was added, and the mixture was stirred at 60 ° C for 4 hr. After completion of the reaction, water was added to the reaction mixture, the target compound was extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 3.2 g of the target compound as a colorless oily liquid.

¹ H-NMR (CDCl ₃ , δppm) 1.60-1.71 (3H, d-d), 2.28 (3
H, s), 2.83 to 2.88 (2H, t), 3.71.
Up to 3.79 (2H, m), 4.29 to 4.38 (2H,
q), 5.48 to 5.62 (1H, m), 5.72 to
6.00 (1H, dq), 6.73 to 7.04 (3
H, m), 8.54 (1H, s)

(21) Other compounds (1) in Tables 2 to 17
Synthesis of Other compounds (1) in Tables 2 to 17 were synthesized according to the methods described in (1) to (20) above. The compounds synthesized as described above are shown in Tables 2 to 17.

[0137]

[Table 2]

[0138]

[Table 3]

[0139]

[Table 4]

[0140]

[Table 5]

[0141]

[Table 6]

[0142]

[Table 7]

[0143]

[Table 8]

[0144]

[Table 9]

[0145]

[Table 10]

[0146]

[Table 11]

[0147]

[Table 12]

[0148]

[Table 13]

[0149]

[Table 14]

[0150]

[Table 15]

[0151]

[Table 16]

[0152]

[Table 17]

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, and then granulated and dried to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 1, 67.5 parts by weight of kaolin, 20 parts by weight of white carbon, 2 parts by weight of neoperex powder (trade name; manufactured by Kao Corporation) and demol (product) Name; made by Kao Co., Ltd.) and 0.5 parts by weight, and
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of Compound 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 Dust Formulation 5 parts by weight of compound 1, 50 parts by weight of talc and 4 of kaolin
A powder was obtained by uniformly mixing 5 parts by weight.

Example 3 [Efficacy test] (1) Efficacy test against diamondback moth The wettable powder of each compound (1) shown in Tables 2 to 17 prepared according to Example 2 was treated with a surfactant (0.01%). Was diluted to 300 ppm with water containing cabbage, cabbage leaf pieces (5 × 5 cm) were dipped in each of these chemical solutions for 30 seconds, placed in each plastic cup one by one, and air dried. Next, in each of these cups, 10 diamondback moths (third instar larvae) were released, covered, and 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 mortality rate. I asked.

The insecticidal effect is evaluated in four stages (A: 100%, B: less than 100-80%, depending on the range of mortality).
C: less than 80 to 60%, D: less than 60%). Incidentally, Comparative Compounds 1 to 3 and JP 5-2019 described in JP-A-59-366666, as shown in Table 18.
Comparative compounds 4 to 7 described in Japanese Patent Publication No. 99 were examined in the same manner as in the case of the compound (1), and were used as comparative examples.

[0159]

[Table 18]

The results are shown in Table 19.

[0161]

[Table 19]

(2) Efficacy test against brown planthopper The respective wettable powders of the compound (1) shown in Tables 2 to 17 prepared according to Example 2 were adjusted to 300 ppm with water containing a surfactant (0.01%). Diluted, rice seedlings were immersed in each of these chemical solutions for 30 seconds, air-dried, and then inserted into each glass cylinder. Next, 10 cylindrical brown planthoppers (4th instar larvae) were left in each cylinder, capped with a porous plug, allowed to stand in a constant temperature room at 25 ° C., and after 4 days, the number of live and dead insects was counted to determine the insecticidal rate.
The results of evaluation of the insecticidal effect are shown in Table 20 by the comparative compound described in (1) above and the evaluation method of four stages.

[0163]

[Table 20]

(3) Efficacy test against green leafhoppers Each wettable powder of the compound (1) shown in Tables 2 to 17 prepared according to Example 2 was adjusted to 300 ppm with water containing a surfactant (0.01%). Diluted, rice seedlings were immersed in each of these chemical solutions for 30 seconds, air-dried, and then inserted into each glass cylinder. Next, add the green leafhopper (4
10 instar larvae were released, capped with a porous plug, allowed to stand in a constant temperature room at 25 ° C., and after 4 days, the number of live and dead insects was counted to determine the insecticidal rate. The results of evaluation of the insecticidal effect are shown in Table 21 by the comparative compound described in (1) above and the evaluation method of four stages.

[0165]

[Table 21]

(4) Efficacy test against adult female adults of Nite spider Mite [0166] Each wettable powder of compound (1) shown in Tables 2 to 17 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 15 seconds each. Next, each leaf piece was 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 evaluation of the acaricidal effect is carried out in four stages (A: 100%, B: less than 100 to 80 depending on the range of the acaricidal rate).
%, C: less than 80 to 60%, D: less than 60%). The results of evaluation of the acaricidal effect are shown in Table 22 together with the evaluation method described above and the comparative compound described in (1) above.

[0168]

[Table 22]

(5) Efficacy test against sweet potato root-knot nematodes Each wettable powder of the compound (1) shown in Tables 2 to 17 prepared according to Example 2 was adjusted to 10 ppm with water containing a surfactant (0.01%). After dilution, 100 sweet potato nematode nematodes (second stage larvae) were released in each of these drug solutions. 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 to determine the nematicidal rate. The results of the evaluation of the nematicidal effect are 4 stages (A: 100-
90%, B: less than 90 to 80%, C: less than 80 to 60
%, D: less than 60%). Table 23 shows these results.
Shown in.

[0170]

[Table 23]

(6) Control efficacy test against barley powdery mildew (preventive effect) Ten barley (cultivar: black wheat) was grown in a plastic flower pot with a diameter of 6 cm, and seedlings at 1.5 leaf stage were grown. In addition, each wettable powder of the compound (1) shown in Tables 2 to 17 prepared according to Example 2 was mixed with a surfactant (0.01
%), And each of these chemical solutions was 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 conidia spores were collected from the diseased leaves and sprinkled evenly over the plants 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 is carried out in 6 stages (0: whole disease, 1: lesion area is about 60%, 2: lesion area is about 40%, as compared with the degree of lesions in the untreated section. 3: The lesion area is about 20%, 4: The lesion area is 10% or less, and 5: No lesion). The results are shown in Table 24.

[0173]

[Table 24]

(7) Control Efficacy Test Against Wheat Leaf Rust (Preventive Effect) Ten wheats (cultivar: Kobushi wheat) were cultivated in a plastic flower pot with a diameter of 6 cm, and the seedlings were grown at 1.5 leaf stage. A wettable powder of the compound (1) shown in Tables 2 to 17 prepared according to Example 2 was mixed with a surfactant (0.01
%) And dilute to 500 ppm with water containing 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 spores / ml) were uniformly spray-inoculated on the plants. After inoculation, the seedlings were grown in a glass greenhouse for 1 week, and the degree of wheat leaf rust lesions appearing on the first leaf was investigated. The result is
Table 25 shows the 6-step evaluation method described in (6).

[0175]

[Table 25]

[0176]

INDUSTRIAL APPLICABILITY The novel 4-phenethylaminopyrimidine derivative of the present invention has excellent effects such as insecticidal, acaricidal, bactericidal and nematicidal.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinori Yamanaka 5 1978, Kobugushi, Ube City, Yamaguchi Prefecture Ube Kosan Co., Ltd. Ube Laboratory

Claims (3)

[Claims] 1. The following formula (1): (In the formula, R ¹ represents a halogen atom, a hydroxyl group, an acyloxy group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, and a carbon atom having 1 to 4 carbon atoms. Alkylthio group, benzyloxycarbonyloxy group, C2-5 alkyloxycarbonyloxy group, C1-4 alkylsulfonyloxy group, tri (C1-4 alkyl) silyloxy group, or carbon R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or 1 to 4 carbon atoms. Haloalkyl group, haloalkoxy group having 1 to 4 carbon atoms, unsubstituted or halogen atom, 1 to 4 carbon atoms
Benzoyl group, hydroxyl group, carbon having at least one alkyl group, C1-4 alkoxy group, C1-4 haloalkoxy group, C1-4 alkylthio group as a substituent A haloalkylcarbonyl group having 2 to 5 carbon atoms, an alkylsulfonyloxy group having 1 to 4 carbon atoms, a haloalkylsulfonyloxy group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, and 1 carbon atom
To 4 alkylsulfinyl groups, C1 to C4 haloalkylsulfinyl groups, tri (C1 to C4 alkyl) silylalkoxy groups, C1 to C4 alkylthio groups, unsubstituted or halogen atoms, Pyridyloxy group having at least one of haloalkyl group having 1 to 4 carbon atoms as a substituent, unsubstituted or halogen atom, carbon number 1
A phenoxy group having at least one of 4 to 4 haloalkyl groups as a substituent, an alkenyloxy group having 2 to 5 carbon atoms, a haloalkenyloxy group having 2 to 5 carbon atoms, an unsubstituted or halogen atom, and at least a hydroxyl group Benzyl group having one as a substituent, 2-phenyl-2-1,3
-Dioxolanyl group, (alkoxy having 1 to 4 carbon atoms)
It represents an iminobenzyl group, a di (alkyl having 1 to 4 carbons) hydrazonobenzyl group, a nitro group, a haloalkylthio group having 1 to 4 carbons, or an alkynyloxy group having 2 to 5 carbons. n represents an integer of 1 to 5. * Represents an asymmetric carbon atom. ) The 4-phenethylamino pyrimidine derivative shown by these. 2. The following formula (2): (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 (3): (In the formula, R ² and n have the same meanings as described in claim 1.)
4. A compound represented by formula (1) according to claim 1, which is reacted with 4-β-phenethylamines represented by
-A method for producing a phenethylaminopyrimidine derivative. 3. The 4- represented by the formula (1) according to claim 1.
A pest control agent for agricultural and horticultural use containing a phenethylaminopyrimidine derivative as an active ingredient.