JPH0647578B2 - Aralkylaminopyrimidine derivatives, a method for producing the same, and insecticides, acaricides and fungicides containing the derivatives as active ingredients - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to an aralkylaminopyrimidine derivative, a method for producing the same, and an insecticide, acaricide and fungicide containing the derivative as an active ingredient. Is.

(Prior Art and Problems Thereof) Several aralkylaminopyrimidine derivatives have been conventionally known. For example, Journal of American Chemical Society (JACS), 8
0, the 2189 (1958), 4-benzylamino -
6-chloropyrimidine and 4-furfurylamino-6-
Chloropyrimidine has been disclosed as a diuretic intermediate, but it does not have insecticidal and acaricidal efficacy.
Further, JP-A-59-36666 discloses an aminopyrimidine derivative represented by the following general formula.

(Wherein R ₁ and R ₂ represent a lower alkyl group or a halogen atom, or R ₁ and R ₂ are combined to represent a trimethylene group or a tetramethylene group; R ₃ represents a hydrogen atom or a lower alkyl group. X represents an alkylene group; Z represents a substituted or unsubstituted phenyl group (the substituents are 1 or 2 selected from halogen, lower alkyl and lower alkoxy), and a furyl group represents a thienyl group. ) The above-mentioned known compounds have bactericidal, insecticidal, acaricidal activity, and, for example, agro-horticulturally important pests such as diamondback moth and spider mites, and cucumber powdery mildew, cucumber anthracnose, tomato phosphorus disease, tomato blight, It is also effective against serious horticultural diseases such as rice blast disease.

However, the activity of these compounds as insecticides and acaricides is not sufficient.

The present inventors have found that insecticides superior to the above-mentioned known compounds
In order to obtain a compound having acaricidal and bactericidal activity, as a result of earnest studies, by replacing the substituent when Z is a phenyl group in the general formula with a specific substituent, insecticide
It was found that the acaricidal activity was remarkably improved, and the present invention was completed.

[Configuration of the Invention] (Means for Solving Problems) The present invention provides the following formula (I): (In the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with halogen; R ₂ and R ₃ are each independently a halogen atom or a lower alkyl group, Is optionally substituted with halogen, lower alkoxy or lower alkylthio; R ₄ represents a hydrogen atom, a halogen atom or a lower alkyl group; Q is a phenyl group, a 5-membered or 6-membered heteromonocyclic group or a condensed heterocycle The phenyl group and the heterocyclic group are substituted with 1 to 3 substituents selected from halogen, nitro, lower alkyl, halo lower alkyl, lower alkoxy, lower alkylthio, lower alkoxyphenyl and phenoxy. Or oxo may be substituted on the heterocyclic group; A is a lower alkylene group, and the alkylene group has 3 carbon atoms. 5 may be substituted with 1 or 2 substituents selected from a cycloalkyl group, a lower alkynyl group and a lower alkyl group, and the lower alkyl group may be substituted with halogen, lower alkoxy or lower alkylthio. B represents a direct bond, an oxygen atom, a sulfur atom, a linear or branched lower alkylene group or a lower alkyleneoxy group, or an acid addition salt thereof, a process for producing them, and the compound. The present invention provides insecticides, acaricides and fungicides as active ingredients.

In the formula (I), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The lower alkyl group refers to a linear or branched alkyl group having 1 to 5 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an amyl group, an isoamyl group, a sec-amyl group, a sec-isoamyl group ( 1,2-dimethylpropyl group) and t-amyl group (1,1-dimethylpropyl group).

The lower alkoxy group refers to a linear or branched alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group and an amyloxy group.

The lower alkylthio group refers to a linear or branched alkylthio group having 1 to 5 carbon atoms. Examples of such an alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group and an amylthio group.

Examples of the cycloalkyl group having 3 to 5 carbon atoms include cyclopropyl group, cyclobutyl group and cyclopentyl group.

The lower alkynyl group means a linear or branched alkynyl group of 2 to 5. Examples of the alkynyl group include an ethynyl group, a propargyl group and a 1-propynyl group.

The lower alkylene group refers to a linear or branched alkylene group having a chain member having 1 to 5 carbon atoms. Such alkylene groups, a methylene group, an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, -CH (CH _{3)
-, - CH (C 2 H} 5) -, - CH (n-C 3 H 7) -, -
_{CH (i-C 3 H 7} ) -, - CH (t-C 4 H 9) -, - C
_{H (n-C 5 H 11} ) -, _{-C (CH 3) 2 -,} - C (CH 3) (C 2 H 5) -, - C
_{H (C 2 H 5) -CH} 2 - and _{-CH (C 2 H 5) -CH} 2 C
H ₂ − and the like can be mentioned.

The lower alkyleneoxy group refers to a linear or branched alkyleneoxy group having a chain member having 1 to 5 carbon atoms. Such alkyleneoxy _group, -OCH 2 _-, - OCH
_{(CH 3) -, - OCH} 2 CH 2 - and -OCH ₂ CH ₂ C
H ₂ − and the like can be mentioned.

R ₁ is preferably a hydrogen atom or a methyl group.

When R ₂ and / or R ₃ is a lower alkyl group,
A methyl group and an ethyl group are preferable, a fluoromethyl group is preferable when it is a lower alkyl group (haloalkyl group) substituted with a halogen atom, and a chlorine atom and a bromine atom are preferable when it is halogen. More preferably, R ₂ is an ethyl group and R ₃ is a chlorine atom, a bromine atom or a methyl group.

R ₄ is preferably a hydrogen atom.

In the above formula (I), Q represents a phenyl group or a heterocyclic group which may be substituted with a specific substituent. Here, the heterocyclic group means all heterocyclic groups containing 1 to 4 heteroatoms in the ring, and particularly 5 or 6-membered heteromonocyclic groups and condensed heterocyclic groups containing these heteromonocyclic groups. Heterocyclic groups are preferred.
Examples of the preferable heterocyclic group include a 5-membered heteromonocyclic group such as a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, an oxadiazolyl group, and a tetrazolyl group; 6-membered heteromonocyclic group such as pyranyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group; benzothiazolyl group,
Examples thereof include condensed heterocyclic groups such as benzoxazolyl group, benzimidazolyl group, thienopyrimidinyl group, furopyrimidinyl group, isoxazolopyrimidinyl group, pyridopyrimidinyl group, quinazolinyl group, quinolyl group and quinoxalinyl group.

When the phenyl group or heterocyclic group represented by Q is substituted, the number of substituents is not particularly limited, but is preferably 1 to 3. As such a substituent, a methyl group, an ethyl group, a t-butyl group, a methyl trihalide group, a methoxy group, a methylthio group, a fluorine atom, a chlorine atom and a nitro group are preferable.

When A is a lower alkylene group substituted with a lower alkyl group, it is preferably a methylene group substituted with a methyl group, an ethyl group, an isopropyl group or an amyl group, and substituted with a cycloalkyl group having 3 to 5 carbon atoms. When it is a lower alkylene group represented by the formula, a methylene group substituted with a cyclopropyl group is preferable.

As B, an oxygen atom and a methylene group are preferable.

The substitution position of the group: -B-Q is 3-position or 4-position with respect to A.
The position is preferred.

Among the above preferred compounds, more preferred compounds are represented by the following formula (I ′): (In the formula, A ′ represents a methylene group substituted with a methyl group, an ethyl group, an isopropyl group or a cyclopropyl group;
Q'is a phenyl group substituted at the 4-position with a fluorine atom, a chlorine atom or a methyl group, or a 2-pyridyl group, 5-chloropyridin-3-yl group, 5-chloro-6-ethylpyrimidin-4-yl. Group, 5-chloro-6-methylpyrimidin-4-yl group or 6-chloro-5-methylpyrimidin-4-yl group; the substitution position of the group: O-Q 'is 3- with respect to A'. Or 4th place. ) Is a compound represented by.

As understood from the above formula (I), the compound of the present invention has an amino group and easily forms an acid addition salt,
Such salts are also included in the present invention.

Acids that form salts include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, carboxylic acids such as formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, aconitic acid. Examples thereof include acids, methanesulfonic acid, benzenesulfonic acid, and organic sulfonic acids such as p-toluenesulfonic acid.

In the above formula (I), when any of the carbon atoms is an asymmetric carbon, the present invention includes any of individual optical isomers and racemates or mixtures.

The compound (I) of the present invention can be easily produced, for example, by a method known per se shown below.

Manufacturing method A (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A, B and Q have the same meanings as described above; X represents a leaving group.) As described above, this reaction is known per se. Therefore, there is no limitation on the leaving group X, for example, a halogen atom such as a chlorine atom, a bromine atom or an iodine atom,
Alkylthio group such as methylthio group, ethylthio group, propylthio group, butylthio group, methanesulfonyloxy group, ethanesulfonyloxy group, alkanesulfonyloxy group optionally substituted with halogen such as trifluoromethanesulfonyloxy group, benzenesulfonyloxy group Group, an arenesulfonyloxy group such as a p-toluenesulfonyloxy group, and a hydroxyl group.

As is clear from the above reaction formula, in this reaction, the compound H-
Since X is released, it is preferable to carry out the reaction in the presence of a base in order to capture this and carry out the reaction smoothly. The reaction is usually performed in the presence of a solvent, but without the solvent, the compound of formula (II)
Alternatively, the compound of formula (III) can be melted by heating.

The solvent is not particularly limited as long as it does not participate in this reaction, for example, benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane,
Chlorinated or unchlorinated aromatic, aliphatic or alicyclic hydrocarbons such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane; diethyl ether, ethylene glycol dimethyl ether, Ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and ethylene glycol, or hydrates thereof; N, N-dimethylformamide (DMF), N, N-dimethyl. Amides such as acetamide; organic bases such as pyridine and N, N-diethylaniline; and mixtures of the above solvents.

As the base, triethylamine, pyridine, N, N-
Examples thereof include organic bases such as diethylaniline, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, inorganic bases such as sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

Although the reaction temperature is not particularly limited, it is usually room temperature or higher and not higher than the boiling point of the solvent used, and it is preferable to heat to shorten the reaction time.

Manufacturing method B (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A, B, Q and X have the same meanings as described above.) In this method, the intermediate (V) is synthesized and then the compound Q-X is synthesized.
This is a method of reacting with (VI). As the solvent, base and the like used in this method, those described in the above-mentioned production method A can be appropriately used.

Production Method C In the above formula (I), the compound in which R ₂ is a lower alkyl group substituted with a lower alkoxy group or a lower alkylthio group can also be produced by the method shown below.

(In the formula, R ₁ , R ₃ , R ₄ , A, B, Q and X are as defined above; D represents a lower alkylene group; R ₅ represents a lower alkoxy group or a lower alkylthio group; M represents Alkali metal, preferably sodium is represented.) Production method D In the above formula (I), Q is a group: The compound which is the same as can also be manufactured by the method shown below.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A, B, Q and X have the same meanings as described above.) The solvent, the base and the like used in this method are the same as those described in the above Production method A. It can be used as appropriate.

In the above production methods A, B, and D, among the compounds of formulas (III) and (IV) used as raw materials, compounds in which the chain member of the lower alkylene group represented by A is 1-substituted by 1 are, for example, It is produced by a method known per se shown below.

(In the formula, R ₄ , A and B are as defined above; R ₆ is a cycloalkyl group having 3 to 5 carbon atoms, a lower alkynyl group or an unsubstituted or halogen atom, a lower alkoxy group or a lower alkylthio group. Represents a substituted lower alkyl group; Q ″ has the same meaning as the above Q or a hydrogen atom.) In the compound of formula (III), the lower alkylene group represented by A has 2 to 5 chain members. A compound is produced, for example, by a method known per se shown below.

(In the formula, R ₄ , R ₆ , B and Q have the same meanings as described above, and m represents an integer of 1 to 4.) Further, among the compounds of the formula (III), compounds in which A is disubstituted are For example, it is produced by a method known per se shown below.

(In the formula, R ₄ , R ₆ , B and Q have the same meanings as described above.) Further, the compounds (III) and (IV) can also be produced by Hofmann decomposition of the corresponding acid amide.

The desired product (I) obtained by each of the above methods can be appropriately purified by a known means such as recrystallization or various chromatography.

The acid addition salt can be easily obtained, for example, by introducing an acid into the reaction solution after the reaction and then removing the solvent.

The compound of the present invention, hemiptera, for example, planthoppers, leafhoppers, aphids, whiteflies, etc., Lepidoptera, for example, beetles, diamondback moths, leaf beetles, leaf moths,
It shows excellent effects against Coleoptera, such as cabbage butterfly, Coleoptera, for example, weevils and beetles, and also against Acarina, for example, agricultural and horticultural harmful insects such as citrus spider mite and spider mites. It is also extremely effective in controlling hygienic pests such as flies, mosquitoes, and cockroaches, and is also effective in other stored-grain pests.

Furthermore, the compounds of the present invention are also effective against root-knot nematodes, pine wood nematodes, and house mites in soil. Also,
The compounds of the present invention are also effective against agricultural and horticultural diseases, and are active against, for example, rice blast disease, barley powdery mildew, cucumber downy mildew, tomato late blight and the like.

As described above, the use and application of the compound of the present invention are extremely wide, high in efficacy, and can be put to practical use in various dosage forms.

The insecticidal, acaricidal and bactericidal agent of the present invention comprises one or several compounds of the general formula (I) as an active ingredient. Although the compound of the general formula (I) may be used as such, it is usually mixed with an ordinary carrier, surfactant, dispersant, auxiliary agent or the like by a conventional method, for example, powder, wettable powder, emulsion, It is prepared and used in a composition such as a fine granule, a granule, a water or oily suspension, an aerosol or the like.

Suitable carriers are, for example, talc, bentonite, clay,
Solid carriers such as kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea,
Kerosene, hydrocarbons such as mineral oil, benzene, toluene, aromatic hydrocarbons such as xylene, chloroform, chlorinated hydrocarbons such as carbon tetrachloride, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, cyclohexanone and isophorone, Examples thereof include esters such as ethyl acetate, ethylene glycol acetate and dibutyl maleate, alcohols such as methanol, n-hexanol and ethylene glycol, polar solvents such as dimethylformamide and dimethyl sulfoxide, and liquid carriers such as water. Further, air, nitrogen, carbon dioxide gas, Freon or the like may be used as the gas carrier, and mixed injection may be performed.

Further, as a surfactant or a dispersant for improving the performance of the present agent such as adhesion to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading, for example, alcohol sulfate ester, alkyl sulfonate , Lignin sulfonate, polyoxyethylene glycol ether and the like are used.

Further, in order to improve the properties of the preparation, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic, etc. are used as an auxiliary agent.

The above-mentioned carrier, surfactant, dispersant and auxiliary agent are used alone or in combination according to the purpose.

The concentration of the active ingredient when the compound of the present invention is formulated is usually 1 to 50% by weight in an emulsion, 0.3 to 25% by weight in a powder, usually 1 to 90% by weight in a wettable powder, and usually 0 in a granule. 0.5 to 5% by weight, usually 0.5 for oil
It is usually from 0.1 to 5% by weight, and with an aerosol it is usually from 0.1 to 5% by weight.

These preparations may be diluted to an appropriate concentration and sprayed on the plant foliage, soil, water surface of paddy fields, or applied directly to them for various purposes according to their respective purposes.

(Examples of the Invention) Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples do not limit the scope of the present invention.

Example 1 dl-5-chloro-6-ethyl-4- (α-ethyl-3
Synthesis of -phenoxybenzyl) aminopyrimidine (Compound No. 3) 1.8 g of 4,5-dichloro-6-ethylpyrimidine was dissolved in 50 m of toluene, 1.1 g of triethylamine and 2.2 g of α-ethyl-3-phenoxybenzylamine were dissolved. Was added and refluxed for 6 hours with stirring. After completion of the reaction, the reaction product was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily matter was subjected to column chromatography (Wakogel C-200, toluene: ethyl acetate = 7:
1 elution) to obtain 2.0 g of the desired product as a flame yellow oily liquid.

▲ n ^21.2 _D ▼ 1.5918 Example 2 dl-5-chloro-6-ethyl-4-[alpha-ethyl-4
Synthesis of-(4-fluorophenoxy) benzyl] aminopyrimidine (Compound No. 41) 1.8 g of 4,5-dichloro-6-ethylpyrimidine was dissolved in 50 m of toluene, and 1.1 g of triethylamine and α-ethyl-4- ( 2.6 g of 4-fluorophenoxy) benzylamine was added, and the mixture was refluxed for 6 hours with stirring. After the reaction was completed, the produced triethylamine hydrochloride was removed, and the solvent was distilled off from the solution under reduced pressure. The obtained oily matter was isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 7: 1 elution) to obtain 1.8 g of the desired product as a pale yellow oily liquid.

N ^21.6 _D 1.5694 Example 3 Synthesis of dl-5-chloro-6-ethyl-4- (α-isopropyl-4-phenoxybenzyl) aminopyrimidine (Compound No. 22) 4,5-dichloro-6- 1.8 g of ethylpyrimidine was dissolved in 50 m of xylene, 1.1 g of triethylamine and α-isopropyl-4-phenoxybenzylamine.2.
4 g was added, and the mixture was refluxed for 7 hours with stirring. After completion of the reaction, the reaction product was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 7: 1 elution) to obtain 2.1 g of the desired product as a pale yellow oily liquid.

N ^23.0 _D 1.5823 Example 4 Synthesis of dl-5-chloro-6-chloromethyl-4- (α-ethyl-3-phenoxybenzyl) aminopyrimidine (Compound No. 10) 6-chloromethyl-4, 5-dichloropyrimidine 2.1
g and toluene 50 m, triethylamine 1.
0 g and α-ethyl-3-phenoxybenzylamine 2.
2 g was added, and the mixture was stirred at 50 to 60 ° C. for 3 hours. After the reaction was completed, the produced triethylamine hydrochloride was removed, and the solvent was distilled off from the solution under reduced pressure. The obtained oily substance was subjected to column chromatography (Wakogel-C200, toluene:
The product was isolated with ethyl acetate = 5: 1 (elution) to obtain 2.8 g of the desired product as a pale yellow oily liquid.

N ^27.6 _D 1.5965 Example 5 synthesis of dl-5-chloro-4- (α-ethyl-3-phenoxybenzylamino) -6-methylthiomethylpyrimidine (Compound No. 12) dl obtained in Example 4 -5-chloro-6-chloromethyl-
2.0 g of 4- (α-ethyl-3-phenoxybenzyl) aminopyrimidine was dissolved in 50 m of methanol, 10 m of a 15% aqueous solution of methanethiol sodium salt was added, and the mixture was refluxed for 2 hours with stirring. After the reaction was completed, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 5: 1 elution) to obtain 1.8 g of the desired product as a pale yellow oily liquid.

N ^27.6 _D 1.6014 Example 6 dl-5-chloro-6-ethyl-4- (α-ethyl-3)
Synthesis of -phenoxybenzyl) aminopyrimidine oxalate dl-5-chloro-6-ethyl-4-obtained in Example 1
0.61 g of (α-ethyl-3-phenoxybenzyl) aminopyrimidine and 0.15 g of oxalic acid were added to 20 m of acetone.
And was heated to reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with n-hexane to obtain 0.7 g of the desired product as a colorless starch syrup.

Example 7 dl-5-chloro-6-ethyl-4- [α-ethyl-4
Synthesis of-(4-fluorophenoxy) benzyl] aminopyrimidine hydrochloride salt dl-5-chloro-6-ethyl-4- obtained in Example 2
1.0 g of [α-ethyl-4- (4-fluorophenoxy) benzyl] aminopyrimidine was added to 20 m of anhydrous ether.
It was dissolved in and was blown with dry hydrochloric acid gas. Ether was removed from the separated oily substance and the product was washed with n-hexane to obtain 1.0 g of the desired product as a colorless starch syrup.

Example 8 Compound Nos. 1, 2, 4 to 9, 11, 13 to 21, 23 to 4 in Table 1 were treated by the same treatment as in Examples 1 to 5.
The compounds shown as 0 and 42-65 were obtained.

Example 9 dl-5-chloro-6-ethyl-4- [α-ethyl-4
-(5-Nitropyridin-2-yloxy) benzyl]
Synthesis of aminopyrimidine (Compound No. 78) 0.9 g of 4,5-dichloro-6-ethylpyrimidine was dissolved in 30 m of toluene, and 0.6 g of triethylamine and α-ethyl-4- (5-nitropyridin-2-yloxy) were dissolved. 1.3 g of benzylamine was added, and the mixture was heated under reflux for 12 hours with stirring. After the reaction was completed, the mixture 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 matter was subjected to column chromatography (Wakogel C-200, toluene: ethyl acetate = 2: 1).
The target compound 0.8 which is a colorless oily liquid.
g was obtained.

N ^22.2 _D 1.5962 Example 10 dl-5-chloro-6-ethyl-4- [α-ethyl-4
Synthesis of-(3-pyridyloxy) benzyl] aminopyrimidine (Compound No. 72) dl-5-chloro-6-ethyl-4- (α-ethyl-4)
2.2 g of (hydroxybenzyl) aminopyrimidine sodium salt was dissolved in 25 m of dry pyridine, 1.1 g of 3-bromopyridine and 1 g of cuprous chloride were added, and the mixture was heated under reflux for 8 hours with stirring under a nitrogen atmosphere. After completion of the reaction, the reaction product was poured into water and extracted with ethyl acetate. Dilute hydrochloric acid,
After washing with water, it was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1 elution) to obtain 0.8 g of the target substance as a colorless oily liquid.

N ^20.5 _D 1.5974 Example 11 dl-5-chloro-6-ethyl-4- [α-ethyl-4
Synthesis of-(2-pyrimidyloxy) benzyl] aminopyrimidine (Compound No. 88) dl-5-chloro-6-ethyl-4- (α-ethyl-4)
-Hydroxybenzyl) aminopyrimidine 1 g DMF
Dissolve in 30 m, add 0.45 g of 2-chloropyrimidine and 0.7 g of anhydrous potassium carbonate, and stir for about 12 hours for about 1 hour.
Heated to 00 ° C. After the reaction was completed, the reaction product was poured into ice water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to column chromatography (Wakogel C-200,
Isolation was performed using toluene: ethyl acetate = 3: 1 (elution) to obtain 0.7 g of the target product as colorless crystals.

mp 110-112 ° C Example 12 dl-5-chloro-6-ethyl-4- [α-ethyl-4
Synthesis of-(5-chloro-6-ethylpyrimidin-4-yloxy) benzyl] aminopyrimidine (Compound No. 82) 4.5 g of 4,5-dichloro-6-ethylpyrimidine was dissolved in 30 m of toluene, and 4 g of triethylamine and α were dissolved. −
1.3 g of ethyl-4-hydroxybenzylamine was added, and the mixture was refluxed for 24 hours with stirring. After the reaction was completed, the mixture 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 isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 3: 1 elution) to obtain 0.8 g of the target substance as a colorless oily liquid.

N ^23.5 _D 1.5738 Example 13 Compound Nos. 66 to 71, 73 to 77, 79 to 81, 83 shown in Table 1 were treated in the same manner as in Examples 9 to 12.
-87 and 89-95 were obtained.

Example 14 5 parts by weight of the compound of Compound No. 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 Atlas) and 2 parts by weight of sodium ligninsulfonate were mixed uniformly. Then, a small amount of water was added, and the mixture was kneaded, then granulated and dried to obtain a granule.

Example 15 5 parts by weight of the compound of Compound No. 69, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Atlas) and 2 parts by weight of sodium ligninsulfonate were uniformly mixed. Then, a small amount of water was added, and the mixture was kneaded, then granulated and dried to obtain a granule.

Example 16 50 parts by weight of the compound of Compound No. 22, 48 parts by weight of kaolin, and 2 parts by weight of neoperex powder (trade name; manufactured by Kao Atlas) were uniformly mixed and then pulverized to obtain a wettable powder.

Example 17 50 parts by weight of the compound of Compound No. 72, 48 parts by weight of kaolin and 2 parts by weight of neoperex powder (trade name; manufactured by Kao Atlas) were uniformly mixed and then pulverized to obtain a wettable powder.

Example 18 Toxanone (trade name; manufactured by Sanyo Chemical Industries) was added to 20 parts by weight of the compound of Compound No. 38 and 70 parts by weight of xylene, and the mixture was uniformly mixed and dissolved to obtain an emulsion.

Example 19 Toxanone (trade name; manufactured by Sanyo Chemical Industries) was added to 20 parts by weight of the compound of Compound No. 81 and 70 parts by weight of xylene, and the mixture was uniformly mixed and dissolved to obtain an emulsion.

Example 20 5 parts by weight of the compound of Compound No. 12, 50 parts by weight of talc, and 45 parts of kaolin were uniformly mixed to obtain a dust.

Example 21 5 parts by weight of the compound of Compound No. 83, 50 parts by weight of talc and 45 parts of kaolin were uniformly mixed to obtain a dust.

Example 22 Efficacy test against Spodoptera litura The compounds shown in Table 1 were prepared according to Examples 16 and 17 and diluted with water containing a surfactant (0.03%) to give 3
It was set to 00 ppm. On the other hand, soybean leaves were laid in a plastic cup having a diameter of 10 cm, and 10 second-instar larvae of Spodoptera litura were tested on the leaves. 5m of spray liquid prepared previously
I sprayed each one. Then, leave it in a constant temperature room at 25 ° C for 2
The number of live and dead insects was investigated day after day to obtain the insecticidal rate. The results are shown in Table 2.

In Table 2, the insecticidal rate of 100% is indicated as 5, and the 99-80% is indicated as 4.

As a control, the following formula: The compound represented by (hereinafter referred to as "compound A") was used.

Example 23 Efficacy test against diamondback moth (organophosphorus resistance) Cabbage leaf pieces (5 cm) in a plastic cup with a diameter of 10 cm
X 5 cm), while the compounds shown in Table 1 were prepared according to Examples 16 and 17, and a surfactant (0.03
%) In water containing 300 ppm, and sprayed with a spray tower at 5 m
I sprayed each one. After air-drying, 10 third-instar larvae of Plutella xylostella were tested and allowed to stand in a constant temperature room at 25 ° C., and the number of live and dead larvae was investigated 2 days later to determine the insecticidal rate. The results are shown in Table 3.

In Table 3, those having an insecticidal rate of 100% are represented by 5, and those having an insecticidal rate of 99-80% are represented by 4.

Example 24 Efficacy test against brown planthopper The compounds shown in Table 1 were prepared according to Examples 16 and 17, and 300 ppm in water containing a surfactant (0.03%).
The rice seedlings were dipped in the above chemical solution for 30 seconds, air-dried,
It was inserted into a glass cylinder. Ten third-instar larvae of the brown planthopper were released, capped with a porous plug, and allowed to stand in a constant temperature room at 25 ° C.
Two days later, the number of live and dead insects was investigated and the insecticidal rate was calculated. The results are shown in Table 4.

Table 4 shows that the insecticidal rate is 100% is 5,99-80%
Are labeled as 4.

Example 25 Efficacy test against leafhopper leafhopper (organic phosphorus agent resistance) The compounds shown in Table 1 were prepared according to Examples 16 and 17, and 300 ppm was added in water containing a surfactant (0.03%).
The rice seedlings were dipped in the above chemical solution for 30 seconds, air-dried,
It was inserted into a glass cylinder. 10 green leafhoppers 4th instar larvae
It was released from the head, capped with a porous plug, and left in a constant temperature room at 25 ° C. Two days later, the number of live and dead insects was investigated and the insecticidal rate was calculated. The results are shown in Table 5.

Table 5 shows that the insecticidal rate is 100%: 5, 99-80%
Are labeled as 4.

Example 26 Efficacy test against adult female mites (organophosphorus drug resistance) of green mites, plaque leaf pieces having a diameter of 20 mm were placed on paper soaked with water,
10 adult females of the tick mites were inoculated. The leaf pieces were formulated with the compounds shown in Table 1 according to Examples 16 and 17,
It was immersed for 15 seconds in a chemical solution containing 300 ppm of water containing a surfactant (0.03%). After air drying, it was left in a constant temperature room at 25 ° C. After 3 days, the number of live and dead insects was investigated and the acaricidal rate was calculated. The results are shown in Table 6.

Table 6 shows that the acaricidal rate is 100%: 5,99-80
% Was shown as 4.

Example 27 Efficacy test against scabbard eggs (organophosphate resistance) Egg leaf pieces with a diameter of 20 mm are placed on paper soaked in water,
Five female adults of Nami-dani mite were inoculated and allowed to lay eggs for 1 day.
Next, the female adults were removed, and the compound shown in Table 1 was prepared according to Examples 16 and 17 together with the kidney bean leaf pieces on which eggs were laid, and the mixture was treated with water containing a surfactant (0.03%). Thirty
It was immersed for 15 seconds in a chemical solution of 0 ppm. After air drying,
It was left in a constant temperature room at 25 ° C. On the 8th day after the treatment, the number of unhatched eggs was examined to determine the ovicidal rate. The results are shown in Table 7.

Table 7 shows that the ovicidal rate is 100% is 5,99-80%
Are labeled as 4.

Example 28 Citrus spp. Female adult (organophosphorus agent resistant)
Efficacy test against mulberry leaf pieces with a diameter of 20 mm were placed on paper soaked with water, and 10 adult citrus mite females were inoculated. On the other hand, the compounds shown in Table 1 were prepared according to Examples 16 and 17, and a chemical solution containing 300 ppm of water containing a surfactant (0.03%) was sprayed in a spray tower at 5 m intervals. After the treatment, the mixture was left in a constant temperature room at 25 ° C., and the number of live and dead insects was examined 3 days later to determine the mortality rate. The results are shown in Table 8.

Table 8 shows that the acaricidal rate is 100%: 5,99-80
% Was shown as 4.

Example 29 Efficacy test for citrus red mite egg (organophosphorus drug resistance) A mulberry leaf piece having a diameter of 20 mm was placed on a paper soaked in water, and 5 female adult citrus red mite were inoculated and allowed to lay eggs for 1 day. On the other hand, the compounds shown in Table 1 were prepared according to Examples 16 and 17, and 300 parts were prepared with water containing a surfactant (0.03%).
The chemical solution in ppm was sprayed on the spray tower at intervals of 5 m. After the treatment, the mixture was allowed to stand in a constant temperature room at 25 ° C. and the number of unhatched eggs after 10 days was examined to determine the egg killing rate. The results are shown in Table 9.

Table 9 shows that the ovicidal rate is 100% is 5,99-80%
Are labeled as 4.

Example 30 Rice blast control effect The soil was put into a plastic pot and seeded with rice. The seedlings cultivated in a greenhouse and having 3.5 true leaves were prepared according to Examples 16 and 17, and a surfactant (0.01
%), And a sufficient amount of the chemical solution diluted to 200 ppm with water was sprayed. 48 hours after spraying, rice blast fungus (Piricularia o
rizae) spore suspension spray inoculated, temperature 25 ℃, humidity 1
After leaving it in a 00% sick box for 4 days, the number of lesions was measured. The drug effect was judged by comparing with the number of lesions in the untreated section.
The evaluation is shown on a scale of 5 to 0, with no lesions being 5, lesion areas less than 10% being 4, 20% being 3, 40% being 2, 60% compared to the untreated section Then, the value was set to 1, and the one which was totally affected was indicated by 0. The results are shown in Table 10.

Example 31 Effect of controlling cucumber downy mildew The soil was put in a plastic pot and the cucumber was sown. Example 1 was applied to seedlings cultivated in a greenhouse and the first leaves were developed.
Prepared according to 6 and 17, surfactant (0.01%)
A sufficient amount of the chemical liquid diluted to 200 ppm with water containing was sprayed. 48 hours after spraying, cucumber downy mildew (Pseudoperon)
ospora cubensis) sprayed and inoculated at a temperature of 20
It was left for 24 hours in a room at 100 ° C. and 100% humidity. Inoculation 10
The lesion area on the day was visually measured and compared with the lesion area of the untreated section to determine the drug effect. Evaluation is shown in 5 stages of 5-0,
No lesions 5; lesion area 10 compared to untreated plot
% Or less is 4, 20% is 3, 40% is 2, 60
About 1%, it was set to 1, and those infected with the whole disease were shown to be 0.
The results are shown in Table 11.

Example 32 Effect of controlling barley powdery mildew The soil was put into a plastic pot and seeded with barley.
The seedlings cultivated in a greenhouse and having the second leaves developed were prepared according to Examples 16 and 17, and a sufficient amount of a chemical solution diluted to 200 ppm with water containing a surfactant (0.01%) was sprayed. 48 hours after spraying, barley powdery mildew (Erysiphe gramini)
s) The spore suspension was uniformly spray-inoculated. The number of lesions was calculated 7 days after the inoculation to determine the drug effect. The evaluation is shown on a scale of 5 to 0, 5 without lesions, 4 with a diseased area of 10% or less,
About 20% is 3, about 40% is 2, about 60% is 1
It was shown as 0 in the case of the whole diseased. First result
The results are shown in Table 2.

[Effects of the Invention] According to the present invention, it is possible to provide a novel aralkylaminopyrimidine derivative having an excellent insecticidal effect, acaricidal effect and bactericidal effect.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C07D 409/12 239 8829-4C 413/12 239 8829-4C 417/12 239 9051-4C (72) Inventor Satoshi Fujii 5 1978, Oji, Kobe, Ube City, Yamaguchi Prefecture Ube Research Co., Ltd., Ube Laboratory (72) Inventor Haruo Yoshiya 5 1978, Kobe, Obe City, Yamaguchi Prefecture Ube Laboratory, Inc. (72) Inventor Kiyouchi Kiyoshi 5 1978, Kobugushi, Ube City, Ube City 5 Ube Kosan Co., Ltd. Ube Laboratory

Claims (5)

[Claims] 1. The following formula: (In the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with halogen; R ₂ and R ₃ are each independently a halogen atom or a lower alkyl group, Is optionally substituted with halogen, lower alkoxy or lower alkylthio; R ₄ represents a hydrogen atom, a halogen atom or a lower alkyl group; Q is a phenyl group, a 5-membered or 6-membered heteromonocyclic group or a condensed heterocycle The phenyl group and the heterocyclic group are substituted with 1 to 3 substituents selected from halogen, nitro, lower alkyl, halo lower alkyl, lower alkoxy, lower alkylthio, lower alkoxyphenyl and phenoxy. Or oxo may be substituted on the heterocyclic group; A is a lower alkylene group, and the alkylene group has 3 carbon atoms. 5 may be substituted with 1 or 2 substituents selected from a cycloalkyl group, a lower alkynyl group and a lower alkyl group, and the lower alkyl group may be substituted with halogen, lower alkoxy or lower alkylthio. B represents a direct bond, an oxygen atom, a sulfur atom, a linear or branched lower alkylene group or a lower alkyleneoxy group, or an acid addition salt thereof. 2. The following formula: (In the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with halogen; R ₂ and R ₃ are, independently of each other, a halogen atom or a lower alkyl group; Is optionally substituted with halogen, lower alkoxy or lower alkylthio; X represents a leaving group), a compound represented by the following formula: (In the formula, R ₄ represents a hydrogen atom, a halogen atom or a lower alkyl group; Q represents a phenyl group, a 5-membered or 6-membered heteromonocyclic group or a condensed heterocyclic group, and these phenyl group and heterocyclic group May be substituted with 1 to 3 substituents selected from halogen, nitro, lower alkyl, halo lower alkyl, lower alkoxy, lower alkylthio, lower alkoxyphenyl and phenoxy, and the heterocyclic group may be oxo. May be substituted; A is a lower alkylene group, and the alkylene group has 1 or 2 substituents selected from a cycloalkyl group having 3 to 5 carbon atoms, a lower alkynyl group and a lower alkyl group. It may be substituted, and the lower alkyl group may be substituted with halogen, lower alkoxy or lower alkylthio; B is a direct bond, an oxygen atom, Ou atom, the formula that comprises reacting with a compound represented by the representative) a linear or branched lower alkylene group or a lower alkyleneoxy group.: (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A, B and Q have the same meanings as described above.) A method for producing a compound or an acid addition salt thereof. 3. The following formula: (In the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with halogen; R ₂ and R ₃ are each independently a halogen atom or a lower alkyl group, Is optionally substituted with halogen, lower alkoxy or lower alkylthio; R ₄ represents a hydrogen atom, a halogen atom or a lower alkyl group; Q is a phenyl group, a 5-membered or 6-membered heteromonocyclic group or a condensed heterocycle The phenyl group and the heterocyclic group are substituted with 1 to 3 substituents selected from halogen, nitro, lower alkyl, halo lower alkyl, lower alkoxy, lower alkylthio, lower alkoxyphenyl and phenoxy. Or oxo may be substituted on the heterocyclic group; A is a lower alkylene group, and the alkylene group has 3 carbon atoms. 5 may be substituted with 1 or 2 substituents selected from a cycloalkyl group, a lower alkynyl group and a lower alkyl group, and the lower alkyl group may be substituted with halogen, lower alkoxy or lower alkylthio. B is a direct bond, an oxygen atom, a sulfur atom, a linear or branched lower alkylene group or a lower alkyleneoxy group) or an acid addition salt thereof as an active ingredient. 4. The following formula: (In the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with halogen; R ₂ and R ₃ are each independently a halogen atom or a lower alkyl group, Is optionally substituted with halogen, lower alkoxy or lower alkylthio; R ₄ represents a hydrogen atom, a halogen atom or a lower alkyl group; Q is a phenyl group, a 5-membered or 6-membered heteromonocyclic group or a condensed heterocycle The phenyl group and the heterocyclic group are substituted with 1 to 3 substituents selected from halogen, nitro, lower alkyl, halo lower alkyl, lower alkoxy, lower alkylthio, lower alkoxyphenyl and phenoxy. Or oxo may be substituted on the heterocyclic group; A is a lower alkylene group, and the alkylene group has 3 carbon atoms. 5 may be substituted with 1 or 2 substituents selected from a cycloalkyl group, a lower alkynyl group and a lower alkyl group, and the lower alkyl group may be substituted with halogen, lower alkoxy or lower alkylthio. B represents a direct bond, an oxygen atom, a sulfur atom, a linear or branched lower alkylene group or a lower alkyleneoxy group) or an acid addition salt thereof as an active ingredient. . 5. The following formula: (In the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with halogen; R ₂ and R ₃ are each independently a halogen atom or a lower alkyl group, Is optionally substituted with halogen, lower alkoxy or lower alkylthio; R ₄ represents a hydrogen atom, a halogen atom or a lower alkyl group; Q is a phenyl group, a 5-membered or 6-membered heteromonocyclic group or a condensed heterocycle The phenyl group and the heterocyclic group are substituted with 1 to 3 substituents selected from halogen, nitro, lower alkyl, halo lower alkyl, lower alkoxy, lower alkylthio, lower alkoxyphenyl and phenoxy. Or oxo may be substituted on the heterocyclic group; A is a lower alkylene group, and the alkylene group has 3 carbon atoms. 5 may be substituted with 1 or 2 substituents selected from a cycloalkyl group, a lower alkynyl group and a lower alkyl group, and the lower alkyl group may be substituted with halogen, lower alkoxy or lower alkylthio. B represents a direct bond, an oxygen atom, a sulfur atom, a linear or branched lower alkylene group or a lower alkyleneoxy group, or a bactericide containing an acid addition salt thereof as an active ingredient.