JPH11302261A - 5-iodo-4-phenethylaminopyrimidine derivative, its production and pesticide for agriculture and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having extreme insecticidal, acaricidal, nematicidal and bacteriocidal activities and useful as a pesticide for agriculture and horticulture. SOLUTION: This new compound is the compound of formula I [R<1> is a halogen, hydroxy or the like; R<2> is H, a 1-4C alkyl or the like; (n) is 1-3; (*) represents an asymmetric carbon atom], e.g. 6-(1-fluoroethyl)-5-iodo-4-(2- phenylethylamino)pyrimidine. The compound of formula I is obtained by reacting pyrimidines of formula II with phenethylamines of formula III in a solvent in the presence of a base. An organic base such as triethylamine is preferable as the base. The reaction is preferably carried out by using the compound of formula III in an amount of 1-1.1 molar times as much as the amount of the compound of formula II at 60-110 deg.C. the reaction time is ordinary 0.5-5 hr. The concentration of an active ingredient when forming the compound of formula I into a preparation is ordinary 1-50 wt.% in a case of an emulsion, 0.3-25 wt.% in a case of a powder, 1-90 wt.% in a case of a wettable powder and 0.5-5 wt.% in a case of a granule or an oil solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 5-iodo-4-phenethylaminopyrimidine derivative which is useful as a pesticide for agricultural and horticultural use.

[0002]

2. Description of the Related Art As a 4-phenethylaminopyrimidine derivative similar to the present invention, there is JP-A-7-258223. However, a 4-phenethylaminopyrimidine derivative in which the 5-position of the pyrimidine ring is substituted with an iodine atom as in the present invention. Disclosure is not allowed. Therefore, the 5-iodo-4 of the present invention
-Phenethylaminopyrimidine derivatives are novel compounds and are not known to have agricultural and horticultural pest control activity.

[0003]

An object of the present invention is to provide a novel 5-iodo-4-phenethylaminopyrimidine derivative, a process for producing the same, and a pesticidal composition for agricultural and horticultural use containing the same as an active ingredient. is there.

[0004]

Means for Solving the Problems The present inventors have studied to solve the above-mentioned problems, and as a result, have found a novel 5-iodo-amine.
The present inventors have found that a 4-phenethylaminopyrimidine derivative has remarkable insecticidal, acaricidal, nematicidal and fungicidal activities for agricultural and horticultural use, and completed the present invention. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0005]

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[0006] (In the formula, R ¹ represents a halogen atom, 2-4 acyloxy group or a hydroxyl carbon atoms; R ²
Is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a haloalkoxy having 1 to 4 carbon atoms. N represents an integer of 1 to 3; * represents an asymmetric carbon atom. )), And a 5-iodo-4-phenethylaminopyrimidine derivative. The second invention provides the following formula (2):

[0007]

Embedded image (In the formula, R ¹ and * are as defined above.)

A pyrimidine represented by the following formula (3):

[0009]

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Wherein R ² and n have the same meanings as defined above, and react with phenethylamines represented by the formula (1).
The present invention relates to a method for producing a 4-phenethylaminopyrimidine derivative. The third invention relates to a pesticide for agricultural and horticultural use containing a 5-iodo-4-phenethylaminopyrimidine derivative represented by the above formula (1) as an active ingredient.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The various substituents represented by the above compounds are as follows. [R ¹ ] R ¹ is a halogen atom, an acyloxy group having 2 to 4 carbon atoms or a hydroxyl group. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; a chlorine atom and a fluorine atom are preferred. As the acyloxy group having 2 to 4 carbon atoms,
Mention may be made of those having a linear or branched alkyl group; acetyloxy groups are preferred.

[R ² ] R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
It is a 4-haloalkyl group, an alkoxy group having 1 to 4 carbon atoms or a haloalkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom for R ² include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; a chlorine atom and a fluorine atom are preferred. 1 carbon atom
Examples of the four alkyl groups include a linear or branched alkyl group; a methyl group is preferred. Examples of the haloalkyl group having 1 to 4 carbon atoms include a trifluoromethyl group, a 2,2,2-trifluoroethyl group,
-Fluoroethyl group and the like; more preferably, trifluoromethyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms include straight or branched ones;
Preferably, it is a methoxy group. Examples of the haloalkoxy group having 1 to 4 carbon atoms include a difluoromethoxy group,
Examples thereof include a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group and a 2-fluoroethoxy group; more preferably, a trifluoromethoxy group and a 2,2,2-trifluoroethoxy group. . R ²
Are preferably the m-position and the p-position. [N] n represents an integer of 1 to 3, and is preferably 1 or 2.

Since the compound (1) of the present invention has an amino group, an acid addition salt derived therefrom is also included in the present invention. Examples of the acid forming an acid addition salt include hydrochloric acid,
Inorganic acids such as hydrobromic acid, nitric acid, sulfuric acid and phosphoric acid; formic acid,
Examples thereof include carboxylic acids such as oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, and aconitic acid; sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; and saccharin. Further, since the compound (1) of the present invention contains an asymmetric carbon atom indicated by *, individual optical isomers derived therefrom,
Both the racemate and mixtures thereof are included in the present invention.

As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned. From the viewpoint of drug efficacy, the following compounds are preferred. (1) The compound (1) in which R ¹ is a halogen atom and R ² is a hydrogen atom. (2) The compound (1) wherein R ¹ and R ² are a halogen atom and n is 1. (3) The compound (1) in which R ¹ is an acyloxy group having 2 to 4 carbon atoms and R ² is a hydrogen atom. (4) R ¹ is a halogen atom, and R ² is carbon atom 1
A compound (1) in which n is 1 to 4 alkyl groups. (5) R ¹ is a halogen atom and R ² is 1 carbon atom
A compound (1) in which n is 1 to 4 alkoxy groups. (6) R ¹ is a halogen atom, and R ² is a group having 1 carbon atom
A compound (1) in which n is 1 to 4 haloalkoxy groups;

[Synthesis of Compound (1)] The above formula (1)
As a preferable method for producing a 5-iodo-4-phenethylaminopyrimidine derivative represented by the following formula, in addition to the synthesis method 1 described as the second invention, the following four types of production methods (synthesis methods 2 to 5) are mentioned. be able to. (Synthesis method 2) The following formula (1-1):

[0017]

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(Wherein R ² , n and * have the same meanings as described above; R ³ represents a chlorine atom or a bromine atom.) 4-phenethylaminopyrimidine derivative [compound (1-1) Name. And the following equation (4):

[0019]

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[0020] (wherein, R ⁴ represents. A lower acyloxy group) represented by the formula (1) in at by R ¹ is a lower acyloxy group which comprises reacting a lower aliphatic carboxylic acid represented by 5-iodo-4-phenethylaminopyrimidine derivative [referred to as compound (1-2)]. ] Manufacturing method. (Synthesis method 3) The following formula (1-2):

[0021]

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(Wherein, R ² , R ⁴ , n and * have the same meanings as described above) [Compound (1-2) and the following formula (5):

[0023]

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(Wherein, M represents an alkali metal)
Before reacting with the indicated inorganic bases
In the formula (1), R ¹Is 5-iodo, which is represented by a hydroxyl group
-4-phenethylaminopyrimidine derivative [compound (1
-3). ] Manufacturing method. (Synthesis method 4) The following formula (1-3):

[0025]

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(Wherein R ² , n and * have the same meanings as described above). 4-phenethylaminopyrimidine derivative [referred to as compound (1-3)]. And the following equation (6):

[0027]

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A fluorinating agent (diethylaminosulfur trifluoride: DAST) represented by the formula (1), wherein R ¹ is 5-iodo-4-phenethylamino in the above formula (1). Pyrimidine derivative [referred to as compound (1-4)]. ] Manufacturing method. (Synthesis method 5) The following formula (1-1):

[0029]

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(Wherein, R ² , R ³ , n and * have the same meanings as described above). 4-phenethylaminopyrimidine derivative [referred to as compound (1-1). And the following equation (7):

[0031]

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(Wherein M is as defined above) and
In the above formula (1), R ¹
Is a 5-iodo-4-phenethylaminopyrimidine derivative represented by a fluorine atom [referred to as compound (1-4). ]
Recipe.

Synthesis method 1 of the above-mentioned compound (1) of the present invention
5 will be described in further detail. (Synthesis Method 1) The synthesis method 1 comprises the compound (2) and the compound (3)
Is reacted in the presence of a base in a solvent to obtain a compound (1). The type of the solvent is not particularly limited as long as it does not directly participate in the reaction.For example, benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, chloroform, dichloroethane, Chlorinated or unchlorinated aromatic, aliphatic and cycloaliphatic hydrocarbons such as trichloroethylene; ethers such as tetrahydrofuran, siloxane, diethyl ether and the like; nitriles such as acetonitrile, propionitrile and the like , Aprotic polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, sulfolane, N, N-dimethylimidazolidinone, N-methylpyrrolidone, etc .; Mixing of the solvent Or the like can be mentioned things.

The amount of the solvent used is such that the compound (2) is 5-80.
Weight percent can be used; however, 10
~ 70% by weight is preferred. The type of base is not particularly limited, and organic and inorganic bases, for example, tertiary amines such as triethylamine, organic bases such as DBU, hydrides, hydroxides, carbonates of alkali metals and alkaline earth metals, Mention may be made of inorganic bases such as hydrogen carbonate; organic bases such as triethylamine are preferred. The amount of the base to be used is 1 to 5 moles compared to the compound (2); preferably 1.2 to 2.0 moles.

The reaction temperature is not particularly limited, but is in the range from room temperature to the boiling point of the solvent used or less;
110 ° C. is preferred. The reaction time varies depending on the above concentration and temperature; it is usually 0.5 to 5 hours. The amount of the starting compound used is the compound (3) based on the compound (2).
Is 1.0 to 5 times mol; preferably 1 to 1.1 times mol. Compound (2) used in the present invention is disclosed in
It can be produced by the method shown in the following formula according to the description of Japanese Patent No. 94417.

[0036]

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(Wherein R ³ , R ⁴ , M and * have the same meanings as above; DAST represents diethylaminosulfur trifluoride.) Compound (8) is prepared, for example, from Journal of Chemical Society ( JCS) 3478-3481 (195
According to the method described in 5), it can be produced by the method shown in the following formula.

[0038]

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Compound (3) can be a commercially available product or can be produced by the method shown in the following formula.

[0040]

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(Wherein R ² and n have the same meanings as described above). After completion of the reaction, the target compound (1) produced as described above is subjected to a conventional method such as extraction, concentration, filtration and the like. Post-treatment can be performed, and if necessary, purification can be appropriately performed by known means such as recrystallization and various types of chromatography.

(Synthesis Method 2) In the synthesis method 2, the compound (1-
The compound (1) is reacted with the compound (4) in a solvent to give the compound (1).
-2) wherein R ¹ in compound (1) has 2 to 4 carbon atoms
A compound having two acyloxy groups).
Examples of the type of the solvent include ethers, ketones, amides such as N, N-dimethylacetamide described in Synthesis Method 1, 1,3-dimethyl-2-imidazolidone, sulfolane, dimethyl sulfoxide; And amides of N, N-dimethylformamide are preferred. The amount of the solvent used depends on the amount of the compound (1-
1) can be used in an amount of 5 to 80% by weight; however, 10 to 70% by weight is preferable. Examples of the type of the base include the inorganic bases described in Synthesis Method 1; potassium carbonate is preferred.

The amount of the base to be used is 1 to 5 moles per 1 mole of Compound (1-1); preferably 2 to 5 moles. The reaction temperature is not particularly limited, but is in the temperature range from room temperature to the boiling point of the solvent to be used or less; The reaction time varies depending on the above-mentioned concentration and temperature; it is 0.5 to 8 hours. As the compound (4), a commercially available product can be used. After completion of the reaction, the target compound (1-2) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and, if necessary, to a known method such as recrystallization or various types of chromatography. It can be appropriately purified by means.

(Synthesis Method 3) In the synthesis method 3, the compound (1-
2) is reacted with compound (5) in a solvent to give compound (1).
-3). Examples of the type of the solvent include ethers, ketones, amides, alcohols (methanol, ethanol, propanol, butanol, and the like), water, and a mixture of the above solvents, as described in Synthesis Method 1. (Methanol, ethanol)
And a mixture of water. The amount of the solvent used depends on the amount of the compound (1
-2) may be used in an amount of 5 to 80% by weight; however, 10 to 70% by weight is preferable.

Examples of the compound (5) include the inorganic bases described in Synthetic Method 1, which are commercially available products; sodium hydroxide and potassium hydroxide are preferred. The amount of the base to be used is 1 to 2 moles compared to Compound (1-2);
1- to 1.5-fold molar is preferred. The reaction temperature is in the temperature range from 0 ° C. to room temperature; room temperature is preferred. The reaction time is
It varies depending on the concentration and temperature as described above; The target compound (1) produced as described above
In the step (-3), after the completion of the reaction, ordinary post-treatments such as extraction, concentration, and filtration are performed, and if necessary, purification can be appropriately performed by known means such as recrystallization and various types of chromatography.

(Synthesis Method 4) The synthesis method 4 comprises the compound (1-
This is a method of reacting 3) with compound (6) in a solvent or without solvent to obtain compound (1-4). Examples of the type of solvent include chlorinated or unchlorinated aromatic, aliphatic, alicyclic hydrocarbons, ethers and the like described in Synthesis Method 1; Aliphatic hydrocarbons are preferred. The amount of the solvent to be used may be such that the compound (1-2) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight. 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 less; 0 ° C. to room temperature is preferred. The reaction time varies depending on the above-mentioned concentration and temperature; it is 0.5 to 1 hour. As the compound (6),
Although not particularly limited, '; the above-mentioned commercially available diethylaminosulfur trifluoride (DAST) is preferred. The amount of compound (6) to be used is 1 to 2 moles compared to compound (1-2); preferably 1 to 1.5 moles. The target compound (1-
In 3), after the reaction is completed, ordinary post-treatments such as extraction, concentration, and filtration are performed, and if necessary, purification can be appropriately performed by known means such as recrystallization and various types of chromatography.

(Synthesis Method 5) This is a method in which compound (1-1) and compound (7) are reacted in a solvent to obtain compound (1-4). Examples of the type of the solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide; 1,3-dimethyl-2-imidazolidone, sulfolane, dimethyl sulfoxide; and a mixture of the above solvents. Can be. The amount of the solvent used depends on the amount of the compound (1
-4) can be used in an amount of from 5 to 80% by weight; however, it is preferably from 10 to 70% by weight. The reaction temperature is not particularly limited, but is in a temperature range from room temperature to the boiling point of the solvent to be used or lower; preferably 100 to 120 ° C. The reaction time varies depending on the concentration and temperature as described above; Examples of the compound (7) include commercially available products such as potassium fluoride, sodium fluoride, and cesium fluoride, and potassium fluoride and cesium fluoride are preferable. Compound (7)
Is 1 to 5 moles compared to Compound (1-1); preferably 1 to 3 moles. After completion of the reaction, the target compound (1-4) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, recrystallization, various chromatography, and other known methods. It can be appropriately purified by means.

[Pest control effect] The pests for agricultural and horticultural use which are controlled by the compound (1) of the present invention include agricultural and horticultural pests such as Hemiptera (hoppers, leafhoppers, aphids, whiteflies, etc.). ), Lepidoptera (Coleoptera, Scarabaeidae, Coleoptera, Pests, Scarabaeidae, White butterfly), Coleoptera (Tenebrionidae, Weevil, Chrysomelidae, Scarabaeidae, etc.), Acaridae (Acari (Acari: Tetranychidae, Tetranychidae), etc.) ), Nematodes (e.g., root-knot nematodes, cyst nematodes, nexare nematodes, singare nematodes, pine wood nematodes), nematodes, sanitary pests (e.g., fly, mosquito, cockroach, etc.), storage pests (e.g. For example, woodpeckers, beetles and the like, wood pests (for example, Termites, termites such as ants, Yamato termites, and termites, beetle bark beetles, leaf beetles, beetles, sink beetles, longhorn beetles, bark beetles, etc., and agricultural and horticultural pathogens (eg, wheat leaf rust, barley udon) Disease, cucumber downy mildew, rice blast, tomato late blight, etc.).

(Pest control agent) The pest control agent for agricultural and horticultural use of the present invention has a particularly remarkable insecticidal / miticidal and nematicidal effect, and contains at least one compound (1) as an active ingredient. It contains. The compound (1) can be used alone, but it is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent and the like (for example, powder, emulsion, fine granule, granule, water Prepared as a composition such as a wetting 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.); Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement in absorption, and dispersion, emulsification and spreading of drugs, include, for example, alcohol sulfates, alkyl sulfates and the like. 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 production of the present agent, the above-mentioned carrier, surfactant, dispersant, and auxiliary can be used alone or in appropriate combination according to the respective purposes. When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions, usually 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 0.1 to 5% by weight for aerosols. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0052]

EXAMPLES The present invention will be specifically described below with reference examples and examples. Note that these do not limit the scope of the present invention. Reference Example 1 (Synthesis method of compound (2)) (1) Synthesis of 4-chloro-6- (1-chloroethyl) -5-iodopyrimidine (1) [compound (2-1)] 4-chloro-6 Ethyl-5-iodopyrimidine (5
g) was dissolved in chloroform (100 ml), and chlorine gas was blown therein while stirring at room temperature. After completion of the reaction, nitrogen gas was blown in to remove excess chlorine gas, and then the solvent was distilled off under reduced pressure. The obtained oil is applied to a silica gel column (Wakogel C).
-200, toluene: ethyl acetate = 20: 1 elution) to obtain 3.4 g of the target compound as a pale yellow oily liquid.

¹ H-NMR (CDCl ₃ , δ ppm) 1.87 to 1.90 (3H, d), 5.54 to 5.51
(1H, q) 8.86 (1H, s)

(2) 6- (1-acetoxyethyl) -4
Synthesis of -chloro-5-iodopyrimidine [compound (2-4)] Dissolve 4-chloro-6- (1-chloroethyl) -5-iodopyrimidine (3.6 g) in N, N-dimethylformamide (70 ml) Then, potassium acetate (2.4 g) and potassium carbonate (0.7 g) were added, and the mixture was heated and stirred at about 60 ° C. for 4 hours. After completion of the reaction, water was added to the reaction mixture, 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 (Wakogel C-gel).
200, toluene: ethyl acetate = 10: 1 elution) to give 1.0 g of the target compound as colorless crystals.

M. p. 55-58 ° C ¹ H-NMR (CDCl ₃ , δ ppm) 1.57-1.60 (3H, d), 2.14 (3H,
s) 5.99-6.09 (1H, q), 8.83 (1H,
s)

(3) Synthesis of 4-chloro-6- (1-hydroxyethyl) -5-iodopyrimidine [compound (2-6)] 6- (1-acetoxyethyl) -4-chloro-5-iodopyrimidine (1.0 g) was dissolved in ethanol (20 ml), and a 1N aqueous solution of sodium hydroxide (20 ml) was stirred.
ml) was added dropwise. After the addition, the mixture was stirred at room temperature for another hour,
The reaction was completed. Then, the solvent was distilled off under reduced pressure, the target compound was extracted with ethyl acetate, washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 20: 1) to obtain 0.5 g of the target substance as a pale yellow oily liquid.

¹ H-NMR (CDCl ₃ , δ ppm) 1.43 to 1.46 (3H, d), 4.13 to 4.16
(1H, m) 5.09-5.17 (1H, q), 8.64 (1H,
s)

(4) Synthesis of 4-chloro-6- (1-fluoroethyl) -5-iodopyrimidine [compound (2-3)] 4-chloro-6- (1-hydroxyethyl) -5-iodopyrimidine (0.5 g) in dichloromethane (20 m
l), diethylaminosulfur trifluoride (0.3 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 was added to the reaction mixture, the dichloromethane layer was separated, 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-
200, eluted with chloroform).
0.4 g of the target substance as a pale yellow liquid was obtained.

1H-NMR (CDCl3, δ ppm) 1.63 to 1.77 (3H, dd), 5.88 to 6.
08 (1H, dq) 8.70 (1H, s)

(5) Synthesis of other compound (2) in Table 1 Other compounds (2) in Table 1 were synthesized according to the methods described in the above (1) to (4). Table 1 shows the compounds (2) synthesized as described above and their physical properties.

[0061]

[Table 1]

(Note) ¹ H-NMR (CDCl ₃ , δ ppm) 2.06 to 2.08 (3H, d), 5.43 to 5.51
(1H, q) 8.84 (1H, s)

Example 1 [Synthesis of Compound (1)] (1) 6- (1-Fluoroethyl) -5-iodo-4-
(2-phenylethylamino) pyrimidine [compound 1]
2-phenylethylamine (0.6 g) and triethylamine (0.6 g) were dissolved in 20 ml of toluene, and 4-chloro-6- (1-fluoroethyl) -5-iodopyrimidine (1.5 g) was added. The mixture was heated and stirred at about 60 ° C. for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (Wakogel C-
200, toluene: ethyl acetate = 10: 1 elution) to obtain 1.1 g of the target compound as pale yellow crystals.
Obtained.

¹ H-NMR (CDCl ₃ , δ ppm) 1.58 to 1.71 (3H, dd), 2.92 to 2.
97 (2H, t) 3.74-3.81 (2H, q), 5.68-5.73
(1H, m) 5.73-5.95 (1H, dq), 7.18-7.
35 (5H, m) 8.48 (1H, s)

(2) Synthesis of 6- (1-chloroethyl) -5-iodo-4- (2-phenylethylamino) pyrimidine [compound 2] 2-phenylethylamine (0.6 g) and triethylamine (0.6 g) Was dissolved in 20 ml of toluene, 4-chloro-6- (1-chloroethyl) -5-iodopyrimidine (1.5 g) was added, and the mixture was heated with stirring at about 60 ° C. for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (Wakogel C-
200, toluene: ethyl acetate = 10: 1 elution) to obtain 1.2 g of the target compound as colorless crystals.

¹ H-NMR (CDCl ₃ , δ ppm) 1.82 to 1.85 (3H, d), 2.92 to 2.97
(2H, t) 3.73-3.83 (2H, m), 5.28-5.35
(1H, q) 5.41 to 5.61 (1H, m), 7.23 to 7.37
(5H, m) 8.46 (1H, s)

(3) 6- (1-acetoxyethyl) -5
Synthesis of -iodo-4- (2-phenylethylamino) pyrimidine [compound 3] 2-phenylethylamine (0.6 g) and triethylamine (0.6 g) were dissolved in 20 ml of toluene, and 4-chloro-6- (1 -Acetoxyethyl) -5-iodopyrimidine (1.7 g) was added, and the mixture was heated with stirring at about 60 ° C for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (Wakogel C).
-200, toluene: ethyl acetate = 10: 1 elution) to obtain 1.2 g of the target substance as a pale yellow liquid.
Obtained.

¹ H-NMR (CDCl ₃ , δ ppm) 1.50 to 1.54 (3H, d), 2.12 (3H,
s) 2.92 to 2.99 (2H, m), 3.74 to 3.82.
(2H, m) 5.54 to 5.70 (1H, m), 5.82 to 5.91
(1H, q) 7.26 to 7.34 (5H, m), 8.55 (1H,
s)

(4) 6- (1-hydroxyethyl) -5
Synthesis of -iodo-4- (2-phenylethylamino) pyrimidine [compound 4] 2-phenylethylamine (0.6 g) and triethylamine (0.6 g) were dissolved in 20 ml of toluene, and 4-chloro-6- (1 -Hydroxyethyl) -5-iodopyrimidine (1.4 g) was added, and the mixture was heated and stirred at about 60 ° C for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (Wakogel C).
-200, toluene: ethyl acetate = 5: 1 elution) to give the target compound as a pale yellow viscous liquid in 1.
0 g was obtained.

¹ H-NMR (CDCl ₃ , δ ppm) 1.39 to 1.44 (3H, d), 2.92 to 2.97
(2H, t) 3.73 to 3.84 (2H, m), 4.13 to 4.20
(1H, m) 4.81 to 4.87 (1H, q), 5.41 to 5.58
(1H, m) 7.22 to 7.37 (2H, m), 8.40 (1H, m)
s)

(5) 6- (1-fluoroethyl) -5
Synthesis of iodo-4- [2- (4-fluorophenyl) ethylamino] pyrimidine [compound 5] 6- (1-fluoroethyl) -5-iodo-4- [2-
(4-Fluorophenyl) ethylamino] pyrimidine (2.0 g) was added to N, N-dimethylformamide (30 m
l), cesium fluoride (1.5 g) was added, and the mixture was heated and stirred at 120 to 130 ° C for 12 hours. After completion of the reaction, water was added, the desired product 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 subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 1).
(0: 1 elution) to give 1.3 g of the desired product as colorless crystals.

¹ H-NMR (CDCl ₃ , δ ppm) 1.59 to 1.72 (3H, dd), 2.89 to 2.
94 (2H, t) 3.71-3.79 (2H, m), 5.41-5.68
(1H, m) 5.68-5.91 (1H, dq), 6.898-
7.05 (2H, m) 7.16 to 7.22 (2H, m), 8.48 (1H, m)
s)

(6) Synthesis of 6- (1-bromoethyl) -5-iodo-4- [2- (4-trifluoromethoxyphenyl) ethylamino] pyrimidine [compound 19] 2- (4-trifluoromethoxyphenyl) ) Ethylamine (1.0 g) and triethylamine (1.0 g) were dissolved in toluene (50 ml), and 4-chloro-6- (1-bromoethyl) -5-iodopyrimidine (1.8 g) was added. The mixture was heated and stirred for 3 hours. After completion of the reaction, the solvent is distilled off under reduced pressure, and the obtained residue is purified by silica gel column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 10: 1) to give the target compound as a pale yellow liquid 1.6 g was obtained.

¹ H-NMR (CDCl ₃ , δ ppm) 1.81 to 1.84 (3H, d), 2.92 to 2.97
(2H, t) 3.72 to 3.79 (2H, q), 5.30 to 5.37
(1H, m) 5.50 to 5.72 (1H, m), 7.17 to 7.27
(4H, m) 8.46 (1H, s)

(7) Synthesis of 6- (1-chloroethyl) -5-iodo-4- [2- (4-trifluoromethoxyphenyl) ethylamino] pyrimidine (compound 20) 2- (4-trifluoromethoxyphenyl) ) Ethylamine (1.0 g) and triethylamine (1.0 g) were dissolved in toluene (50 ml), and 4-chloro-6- (1-chloroethyl) -5-iodopyrimidine (1.5 g) was added. For 3 hours. After completion of the reaction, the solvent is distilled off under reduced pressure, and the obtained residue is purified by silica gel column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 10: 1) to give the target compound as a pale yellow liquid 1.3 g was obtained.

¹ H-NMR (CDCl ₃ , δ ppm) 1.81 to 1.84 (3H, d), 2.92 to 2.97
(2H, t) 3.72 to 3.80 (2H, q), 5.28 to 5.35
(1H, q) 5.56 to 5.73 (1H, m), 7.17 to 7.27
(4H, m) 8.47 (1H, s)

(8) 6- (1-acetoxyethyl)-
Synthesis of 5-iodo-4- [2- (4-trifluoromethoxyphenyl) ethylamino] pyrimidine [compound 21] 6- (1-chloroethyl) -5-iodo-4- [2-
(4-trifluoromethoxyphenyl) ethylamino]
Pyrimidine (1.3 g) was dissolved in DMF (50 ml), and potassium acetate (1.6 g) and potassium carbonate (1.1 g) were dissolved.
g) was added and the mixture was heated and stirred at about 60 ° C. for 3 hours. After the reaction was completed, water was added, and the separated oil was extracted with ethyl acetate.
After the extract was washed with water and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 1.0 g of the target compound as colorless powdery crystals.

¹ H-NMR (CDCl ₃ , δ ppm) 1.50 to 1.53 (3H, d), 2.16 (3H,
s) 2.91-2.95 (2H, t), 3.70-3.79
(2H, q) 5.50 to 5.65 (1H, m), 5.84 to 5.91
(1H, q) 7.16 to 7.27 (4H, m), 8.42 (1H,
s)

(9) 6- (1-hydroxyethyl) -5
Synthesis of -iodo-4- [2- (4-trifluoromethoxyphenyl) ethylamino] pyrimidine [compound 22] 6- (1-acetoxyethyl) -5-iodo-4- [2
-(4-trifluoromethoxyphenyl) ethylamino] pyrimidine (1.0 g) in ethanol (20 ml)
And 1N aqueous sodium hydroxide solution (20 ml)
Was added and stirred at room temperature for 1 hour. After the reaction was completed, water was added, and the separated oil was extracted with ethyl acetate. After the extract was washed with water and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue is subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate =
(1: 1 elution) to obtain 0.9 g of the target compound as a pale yellow liquid.

¹ H-NMR (CDCl ₃ , δ ppm) 1.40 to 1.45 (3H, d), 2.93 to 2.98
(2H, t) 3.73-3.82 (2H, q), 4.08-4.16
(1H, m) 4.82 to 4.89 (1H, q), 5.48 to 5.68
(1H, m) 7.17 to 7.30 (4H, m), 8.40 (1H, m)
s)

(10) 6- (1-fluoroethyl) -5
Synthesis of -iodo-4- [2- (4-trifluoromethoxyphenyl) ethylamino] pyrimidine [compound 23] 6- (1-hydroxyethyl) -5-iodo-4- [2
-(4-Trifluoromethoxyphenyl) ethylamino] pyrimidine (0.9 g) was added to dichloromethane (20 m
l), diethylaminosulfur trifluoride (0.3 g) was added dropwise with cooling and stirring, and the mixture was further stirred for 1 hour. After completion of the reaction, water was added, the chloromethane layer was separated, washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 1: 1) to give 0.6 g of the desired product as colorless powdery crystals.

¹ H-NMR (CDCl ₃ , δ ppm) 1.61 to 1.70 (3H, dd), 2.92 to 2.
98 (2H, t) 3.73-3.81 (2H, m), 5.62-5.66
(1H, m) 5.66-5.91 (1H, dq), 7.16-7.
28 (4H, m) 8.48 (1H, s)

(11) Synthesis of other compound (1) in Tables 2 and 3 According to the method described in the above (1) to (10), the other compound (1) in Tables 2 and 3 was synthesized. did. The compounds (1) synthesized as described above and their physical properties are shown in Tables 2 and 3.

[0084]

[Table 2]

[0085]

[Table 3]

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, Neorex powder (trade name; manufactured by Kao Corporation) 1 Parts by weight and 2 parts by weight of sodium ligninsulfonate were uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying 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 Neolex powder (trade name, manufactured by Kao Corporation), and 0.5 part by weight of Demol (trade name; manufactured by Kao Corporation) is evenly mixed,
Then, it was pulverized to obtain a wettable powder.

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

(4) Preparation of Dust A powder was obtained by uniformly mixing 5 parts by weight of the compound (1), 50 parts by weight of talc and 45 parts by weight of kaolin.

Example 3 [Efficacy test] (1) Efficacy test for sweet potato nematodes Each wettable powder of compound (1) shown in Tables 2 and 3 prepared according to Example 2 was diluted with water to 300 ppm. 0.1 ml was placed in a test tube, and 0.9 ml of a liquid containing 500 sweet potato nematodes was added. Next, these test tubes were allowed to stand in a low-temperature room at 25 ° C. and observed under a microscope two days later to determine the nematicidal rate. As a result, Compounds 1, 5, 9, 13, 17 and 23 showed 100% nematicidal activity.

(2) Tests against Dermatophagoid spider mites The wettable powder of each of the compounds (1) shown in Tables 2 and 3 prepared according to Example 2 was diluted with water containing a surfactant (0.01%) to 300 ppm. Then, in each of these solutions, 15 adult female spider mites were spawned for 24 hours, and then each kidney leaf piece (20 mm in diameter) from which the adult was removed was immersed for 10 seconds. 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 acaricidal rate. As a result, compounds 1, 5, 9, 13,
17 and 23 exhibited acaricidal activity of 80% or more.

(3) Efficacy test for Japanese moths Each wettable powder of compound (1) shown in Tables 2 and 3 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%). Then, cabbage leaf pieces (5 cm × 5 cm) were immersed in each of these chemical solutions for 30 seconds, placed one by one in each plastic cup and air-dried. Next, 10 cups of moth (3rd instar larva) were released into each of these cups, and the cups were capped.
After standing in a constant temperature room at 25 ° C., two days later, the number of live and dead insects in each cup was counted to determine the mortality. As a result, Compounds 1, 3,
5, 9, 13, 17 and 23 showed 100% insecticidal activity.

(4) Efficacy test against brown planthopper Each wettable powder of compound (1) shown in Tables 2 and 3 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 inserted into respective glass cylinders. Next, ten glass brown planthoppers (4th instar larvae) were released into each of these glass cylinders, plugged with a porous plug, and allowed to stand in a constant temperature room at 25 ° C. Was. As a result, Compounds 1, 5, 9, 13, 17, and 23
Showed 100% insecticidal activity.

(5) Efficacy test against leafhopper leafhopper Each wettable powder of compound (1) shown in Tables 2 and 3 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 inserted into respective glass cylinders. Next, ten glass leafhoppers (fourth instar larvae) were released into each of these glass cylinders, plugged with a porous plug, left in a constant temperature room at 25 ° C., and after 4 days, the number of live and dead insects was counted to determine the mortality. Was. As a result, Compounds 1, 5, 9, 13, 17, and 2
3 showed 100% insecticidal activity.

(6) Efficacy test against Spodoptera litura Each wettable powder of compound (1) shown in Tables 2 and 3 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%). Then, the soybean leaf was immersed in each of these chemicals for 30 seconds, air-dried, put in a plastic cup, and each of the 10 cutworm cutworm (second instar larva) was released, capped, and left in a constant temperature room at 25 ° C. Two days later, the number of live and dead insects was counted to determine the mortality. As a result, Compounds 5, 9 and 23
Showed 100% insecticidal activity.

(7) Wheat Rust Control Efficacy Test (Preventive Test) Wheat (cultivar: Kobushi wheat) was grown 10 per pot in a plastic flower pot having a diameter of 6 cm. The wettable powder of the product (1) shown in Tables 2 and 3 prepared according to Example 2 was replaced with a surfactant (0.01%)
Diluted with water containing 500 ppm to 20 m per pot
l. After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then a spore suspension (7 × 10 ⁴ spores / ml) of wheat leaf rust was uniformly spray-inoculated on the plants. After inoculation, the plants were grown for one week in a glass greenhouse, and the degree of wheat leaf rust spots on the first leaves was examined. As a result, Compounds 1, 5,
9, 13, 17, 20, and 23 showed a lesion area of 20% or less.

[0097]

Industrial Applicability The novel 5-iodo-4-phenethylaminopyrimidine derivative of the present invention is useful as a pesticide for agricultural and horticultural use.

Continuation of front page (72) Inventor Yoichi Yoshida 5 Ube Kogushi 1978 Kobe, Ube City, Yamaguchi Prefecture

Claims (3)

[Claims] (1) The following formula (1): (Wherein, R ¹ represents a halogen atom, an acyloxy group having 2 to 4 carbon atoms or a hydroxyl group; R ² represents a hydrogen atom,
A halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a haloalkoxy group having 1 to 4 carbon atoms; n represents an integer of 1 to 3; * represents an asymmetric carbon atom. A) -Iodo-4-phenethylaminopyrimidine derivative represented by the formula: 2. The following formula (2): (Wherein R ¹ and * have the same meanings as described above) and a pyrimidine represented by the following formula (3): (Wherein R ² and n have the same meanings as defined above), and are reacted with phenethylamines represented by the formula (1), wherein 5-iodo-4-phenethylamino is represented by the formula (1). A method for producing a pyrimidine derivative. 3. The compound represented by the formula (1) according to claim 1,
A pesticide for agricultural and horticultural use containing an iodo-4-phenethylaminopyrimidine derivative as an active ingredient.