JPH0625159B2 - 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.

(In the formula, 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), a furyl group or 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 R and ₂ each 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; and R ₄ represents a halogen atom or a lower alkyl. Represents a group; n represents 0, 1 or 2; Q represents 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, carbon Cycloalkyl-methyl group, lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, lower alkylthioethyl group, lower alkylsulfonylethyl group, phenoxyethyl group substituted with 1 or 2 lower alkyl groups, and glycidyl group , Acetonyl group, dioxolanylmethyl group, phenoxymethyl-substituted dioxolane optionally substituted with chlorine atom Nylmethyl group, 2,2-diethoxyethyl group, 1-ethoxycarbonylethyl group, trimethylsilylmethyl group, 1-pyridylethyl group, lower alkoxyiminoalkyl group, or benzyloxyimino whose ring may be substituted with lower alkyl Represents an alkyl group)
The present invention provides a compound represented by or an acid addition salt thereof, a process for producing them, and an insecticide, acaricide and fungicide containing the compound as an active ingredient.

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 alkoxyalkyl group refers to a linear or branched alkoxyalkyl group whose alkoxy moiety has 1 to 5 carbon atoms. Examples of the alkoxyalkyl group include methoxyethyl group, ethoxyethyl group, propoxyethyl group, isopropoxyethyl group, butoxyethyl group, isobutoxyethyl group, sec-butoxyethyl group, t-butoxyethyl group and amyloxyethyl group. Is mentioned.

Examples of the lower alkoxyalkoxyalkyl group include an ethoxyethoxyethyl group.

The lower alkylthioethyl group refers to a linear or branched alkylthioethyl group whose lower alkyl portion has 1 to 5 carbon atoms. Examples of such an alkylthioethyl group include a methylthioethyl group, an ethylthioethyl group, a propylthioethyl group, an isopropylthioethyl group, a butylthioethyl group and an amylthioethyl group.

Examples of the cycloalkyl-methyl group having 3 to 6 carbon atoms include cyclopropylmethyl group, cyclobutylmethyl group and cyclopentylmethyl group.

When R ₁ and / or R ₂ is a lower alkyl group,
A methyl group or an ethyl group is preferable, and when it is a halogen atom, a chlorine atom or a bromine atom is preferable. More preferably, R ₁ is an ethyl group and R ₂ is a chlorine atom or a bromine atom.

When R ₃ is a lower alkyl group, it is preferably a methyl group, an ethyl group or an isopropyl group, and when it is a cycloalkyl group having 3 to 5 carbon atoms, a cyclopropyl group is preferable.

When R ₄ is a halogen atom, a chlorine atom or a bromine atom is preferable, and when it is a lower alkyl group, a methyl group is preferable.

n is preferably 0 or 1. When Q is an alkyl group having 5 to 10 carbon atoms, an isoamyl group or sec-amyl group is preferable; when Q is a lower alkyl group substituted with 1 to 4 halogen atoms, 2-fluoroethyl Base 2,
2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2,2-difluoropropyl group are preferred; lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, lower alkylthioethyl group, lower alkyl In the case of a sulfonylethyl group and a phenoxyethyl group substituted with 1 or 2 lower alkyl, 2-ethoxyethyl group, 2- (2-ethoxyethoxy) ethyl group, 2-ethylthioethyl group, 2 -Ethylsulfonylethyl group is preferable, and when it is a phenoxymethyl-substituted dioxolanylmethyl group optionally substituted with a chlorine atom, 2- (4-chlorophenoxymethyl) dioxolan-4-yl-methyl A group is preferred; when it is a 1-pyridylethyl group, 1- (pyridin-2-yl Ethyl or 1- (pyridin-4
When it is a lower alkoxyiminoalkyl group, a 2-methoxyiminoethyl group or a 2-methoxyiminopropyl group is preferable.

The substitution position of the group: -O-Q is Is preferably 3-position or 4-position.

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 (Wherein R ₁ , R ₂ , R ₃ , R ₄ , n and Q are as defined above; X represents a leaving group.) As mentioned above, this reaction is known per se and 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 the reaction, for example, benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene. Chlorinated or non-chlorinated aromatic, aliphatic or alicyclic hydrocarbons such as cyclohexane; ethers such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane; acetone,
Ketones such as methylethylketone; alcohols such as methanol, ethanol, ethylene glycol, or hydrates thereof; amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide; pyridine, N, Organic bases such as 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 , n, 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), a compound in which Q is an alkyl group substituted with a lower alkoxyimino group or a benzylimino group which may be substituted with a lower alkyl group can also be produced by the following method. it can.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and n have the same meanings as described above; R ₅ represents a hydrogen atom or a lower alkyl group;
₆ represents a lower alkyl group or a benzyl group which may be substituted with a lower alkyl group. ) Production method D In the above formula (I), Q is 1,3-dioxolane-
The compound which is a 2-yl-methyl group can also be produced by the method shown below.

_{(Wherein, R 1, R 2, R} 3, R 4, and n are defined as above; _{R 5} represents a hydrogen atom) METHOD E In Formula (I), Q is 2,2-difluoro The compound which is a propyl group can also be produced by the method shown below.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and n have the same meanings as described above, and R ₅ represents methyl.) In the production methods A and B, the formula (III) used as a raw material, The compound (IV) can be produced, for example, by a method known per se shown below.

(In the formula, R ₃ , R ₄ and n have the same meanings as above; Q has the same meaning as above or a hydrogen atom.) The target product (I) obtained by each of the above methods is recrystallization, various chromatography, etc. It can be appropriately purified by a known method.

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 used after being prepared into a composition such as a fine granule, a powder, a water or oily suspension, or an aerosol.

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 d-5-chloro-6-ethyl-4- [α-ethyl-4
Synthesis of-(isoamyloxy) benzyl] aminopyrimidine (Compound No. 2) d-α-Ethyl-4- (3-methylbutoxy) benzylamine 1.5 g, 4,5-dichloro-6-ethylpyrimidine 1.5 g and 1.2 g of triethylamine was added to 40 m of toluene, and the mixture was heated under reflux for 8 hours with stirring. After completion of the reaction, the solvent was distilled off under reduced pressure, column chromatography (Wakogel C-200), toluene: ethyl acetate =
The product was isolated by elution (7: 1) to obtain 1.1 g of the desired product as a pale yellow liquid.

N ^17.2 _D 1.5444 Example 2 d-5-chloro-6-ethyl-4- [α-ethyl-4
Synthesis of -sec-amyloxy) benzyl] aminopyrimidine (Compound No. 3) d-5-chloro-6-ethyl-4- (α-ethyl-4)
1.1 g of sodium salt of -hydroxybenzyl) aminopyrimidine was dissolved in 30 m of N, N-dimethylformamide, 0.6 g of 2-bromopentane was added, and 90-1
The mixture was stirred at 00 ° C for 8 hours. After the reaction was completed, the reaction solution was added to water, and the oily substance that separated was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and ethyl acetate was evaporated under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 7: 1 elution) to obtain 0.4 g of the desired product as a pale yellow liquid.

N ^20.8 _D 1.5540 Example 3 d-5-chloro-6-ethyl-4- [α-ethyl-4
Synthesis of-(cyclopropylmethoxy) benzyl] aminopyrimidine (Compound No. 11) d-5-chloro-6-ethyl-4- (α-ethyl-4)
1.1 g of -hydroxybenzyl) aminopyrimidine sodium salt was dissolved in 30 m of N, N-dimethylformamide, 0.4 g of cyclopropylmethyl chloride was added, and the mixture was stirred at 90 to 100 ° C for 8 hours. After the reaction was completed, the reaction solution was added to water, and the oily substance that separated was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was evaporated under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 7: 1 elution) to obtain 0.5 g of the desired product as a pale yellow liquid.

▲ n ^19.7 _D ▼ 1.5689 Example 4 d-5-chloro-6-ethyl-4- [α-ethyl-4]
Synthesis of-(1,1,2,2-tetrafluoroethoxy) benzyl] aminopyrimidine (Compound No. 14) d-5-chloro-6-ethyl-4- (α-ethyl-4)
1.6 g of -hydroxybenzylaminopyrimidine sodium salt was dissolved in 30 m of N, N-dimethylformamide, and about 2.2 g of tetrafluoroethylene was slowly blown thereinto at 80 ° C with stirring under a nitrogen stream. After the completion of blowing, the mixture was stirred for 2 hours, the reaction solution was added to water, and the oily substance that separated was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and ethyl acetate was evaporated under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel-C200, toluene: ethyl acetate = 7: 1 elution) to obtain 0.6 g of the desired product as a pale yellow liquid.

N ^15.7 _D 1.5213 Example 5 d-5-chloro-6- (α-ethyl-4-acetonyloxybenzyl) aminopyrimidine (Compound No. 22)
Synthesis of d-5-chloro-6-ethyl-4- (α-ethyl-hydroxybenzyl) aminopyrimidine (3.0 g) with N, N
-Dissolved in 30m of dimethylformamide, added 1.2g of chloroacetone, 1.7g of anhydrous potassium carbonate,
Stirred at 8 ° C for 8 hours. After the reaction was completed, the reaction solution was poured into water, and the oily substance that separated was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and ethyl acetate was evaporated under reduced pressure. The obtained oily substance was isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 7: 1 elution) to obtain the target product 1.
3 g was obtained.

▲ n ^15.6 _D ▼ 1.5654 Example 6 d-5-chloro-6-ethyl-4- [α-ethyl-4]
Synthesis of-(2,2-difluoropropoxy) benzyl] aminopyrimidine (Compound No. 15) d-5-chloro-6-ethyl-4- obtained in Example 4.
1.0 g of (α-ethyl-4-acetonyloxybenzyl) aminopyrimidine, 0.5 g of diethylaminosulfur trifluoride in 50 m of dry benzene,
The mixture was heated under reflux for 5 hours with stirring. After the reaction was completed, the reaction solution was added to ice water and extracted with ethyl acetate. Wash the extract with water,
After drying over anhydrous sodium sulfate, 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 0.2 g of the desired product as a pale yellow oily liquid.

N ^23.8 _D 1.5422 Example 7 d-5-chloro-6-ethyl-4- [α-ethyl-4]
Synthesis of-(2,2-diethoxyethoxy) benzyl] aminopyrimidine (Compound No. 23) d-5-chloro-6-ethyl-4- (α-ethyl-4)
5.0 g of -hydroxybenzyl) aminopyrimidine sodium salt was dissolved in 50 m of N, N-dimethylformamide, 4.8 g of bromoacetaldehyde diethyl acetal was added, and the mixture was stirred at 80 ° C for 8 hours. After the reaction was completed, the reaction solution was added to water, and the oily substance that separated was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and ethyl acetate was evaporated under reduced pressure. The obtained oily substance was subjected to column chromatography (Wako Gel C-200,
It was isolated by toluene: ethyl acetate = 7: 1 elution) to obtain 2.3 g of the desired product as a pale yellow liquid.

N ^16.0 _D 1.5434 Example 8 d-5-chloro-6-ethyl-4- [α-ethyl-4
Synthesis of-(1,3-dioxolan-2-yl-methoxy) benzyl] aminopyrimidine (Compound No. 24) d-5-chloro-6-ethyl-4- obtained in Example 6
[Α-Ethyl-4- (2,2-diethoxyethoxy) benzyl] aminopyrimidine 1.0 g and benzene 60 m
0.5 g of ethylene glycol and a catalytic amount of p-toluenesulfonic acid were added to and heated under reflux for 24 hours with stirring.
After the reaction was completed, the reaction solution was added to ice water and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure. The residue was subjected to column chromatography (Wako Gel C-200, toluene: ethyl acetate =
(7: 1 elution), and the target product is 0.2 as a pale yellow powder.
g was obtained. Melting point 61-63 [deg.] C.

Example 9 d-5-chloro-6-ethyl-4- [α-ethyl-4
Synthesis of-(2-methoxyaminoethoxy) benzyl] aminopyrimidine (Compound No. 27) d-5-Chloro-6-ethyl-4- obtained in Example 6
[Α-Ethyl-4- (2,2-diethoxyethoxy) benzyl) aminopyrimidine (1.0 g) was added to ethanol (40 m).
Dissolved in water, methoxyamine hydrochloride 0.4 g water 8 m
The solution was added. Then, after adding a catalytic amount of 6N hydrochloric acid, the mixture was stirred at 60 ° C. for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, the residue 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 isolated by column chromatography (Wakogel C-200, toluene: ethyl acetate = 7: 1 elution) to obtain 0.4 g of the desired product as a pale yellow liquid.

N ^19.4 _D 1.5678 Example 10 Synthesis of d-5-chloro-6-ethyl-4- [α-isopropyl-4- (2-ethoxyethoxy) benzyl] aminopyrimidine (Compound No. 35) d-5 1.2 g of -chloro-6-ethyl-4- (α-isopropyl-4-hydroxybenzyl) aminopyrimidine sodium salt was added to N, N-dimethylformamide 3
Dissolved in 0m, bromoethyl ethyl ether 0.6
g was added, and the mixture was stirred at 80 ° C. for 8 hours. After the reaction was completed, the reaction solution was added to water, and the oily substance that separated was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and ethyl acetate was evaporated under reduced pressure. The obtained oil was isolated by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 7: 1) to obtain 0.6 g of the desired product as a pale yellow liquid.

N ^25.3 _D 1.5439 Example 11 Compound Nos. 1, 4 to 10, 12, 13, 16 to 22, 2 shown in Table 1 by treating in the same manner as in Examples 1 to 10.
The compounds shown as 5,26,28-34,36-43 were obtained.

Example 12 5 parts by weight of the compound of Compound No. 2, 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 lignin sulfonate 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 13 50 parts by weight of the compound of Compound No. 11, 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 14 Toxanone (trade name; manufactured by Sanyo Chemical Industries) was added to 20 parts by weight of the compound of Compound No. 14 and 70 parts by weight of xylene, and the mixture was uniformly mixed and dissolved to obtain an emulsion.

Example 15 5 parts by weight of the compound of Compound No. 15, 50 parts by weight of talc and 45 parts of kaolin were uniformly mixed to obtain a dust.

Example 16 Efficacy test against Spodoptera litura The compounds shown in Table 1 were prepared according to Examples 12 and 15 and diluted with water containing a surfactant (0.03%) to give 5
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 17 Efficacy test against diamondback moth (organophosphorus resistance) Cabbage leaf pieces (5 cm) in a plastic cup having a diameter of 10 cm
X 5 cm), while the compounds shown in Table 1 were prepared according to Examples 12 and 15, 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 18 Efficacy test against brown planthopper The compounds shown in Table 1 were prepared according to Examples 12 and 15, 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%: 5, 99-80%
Are labeled as 4.

Example 19 Efficacy test against leafhopper leafhopper (organic phosphorus agent resistance) The compounds shown in Table 1 were prepared according to Examples 12 and 15, 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. 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 20 Efficacy test against adult female mites (organophosphorus agent resistance) of green mites, plaque leaf pieces with 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 12 and 15,
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 21 Efficacy test against budworm mites eggs (organic phosphorus resistance) Place bean leaf pieces with a diameter of 20 mm on paper soaked in water,
Five female adults of Nami-dani mite were inoculated and allowed to lay eggs for 1 day.
Next, female adults were removed, and the compound shown in Table 1 was prepared according to Examples 12 and 15 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 22 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 12 and 15, and a chemical solution containing 300 ppm of water containing a surfactant (0.03%) was sprayed in a spray tower at intervals of 5 m. 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 23 Efficacy test for citrus red mite egg (organic phosphorus drug resistance) A mulberry leaf piece having a diameter of 20 mm was placed on a paper soaked in water, and 5 adult citrus mite females 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 12 and 15, and 300 parts were prepared by adding 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 24 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 2 and 15 and 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 10.

Example 25 Control effect of barley powdery mildew The soil was put in a plastic pot and seeded with barley.
The seedlings cultivated in a greenhouse and having the second leaf developed were prepared according to Examples 12 and 15 and sprayed with a sufficient amount of a chemical solution diluted to 200 ppm with water containing a surfactant (0.01%). 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 1.

Example 26 Blast control effect of rice The soil was put in a plastic pot and rice was seeded. For seedlings cultivated in a greenhouse and the true leaves expanded to 3.5 leaves,
The preparation was carried out according to Examples 12 and 15, and the surfactant (0.
A sufficient amount of the chemical liquid diluted to 200 ppm with water containing 0.1%) was sprayed. 48 hours after spraying, rice blast fungus (pir
icularia orizae) spore suspension spray inoculated, temperature 25
After leaving it in a sick box at 100 ° C and 100% humidity 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, where there are no lesions is 5, lesion area is 10% or less compared to the untreated section, 4 is about 20%, 3 is 40%, 2 is 60%. The number was 1 and the number 0 was used when the disease was totally affected. The results are shown in Table 12.

[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 the front page (72) Inventor Satoshi Fujii 5 1978, Ogushi, Ube, Yamaguchi Prefecture 5 1978, Ube Research Co., Ltd. Ube Laboratory (72) Inventor Haruo 5 5 1978, Kobe, Obe, Yamaguchi Prefecture 5 Ube Kosan Ube Institute Co., Ltd. (72) Inventor Kiyoshi Tsutsumi 5 1978, Koujigushi, Ube City, Yamaguchi Prefecture Ube Kosan Co., Ltd. Ube Institute

Claims (5)

[Claims] 1. The following formula: (In the formula, R ₁ and R ₂ each 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; and R ₄ represents a halogen atom or a lower alkyl. Represents a group; n represents 0, 1 or 2; Q represents 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, carbon Cycloalkyl-methyl group, lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, lower alkylthioethyl group, lower alkylsulfonylethyl group, phenoxyethyl group substituted with 1 or 2 lower alkyl groups, and glycidyl group , Acetonyl group, dioxolanylmethyl group, phenoxymethyl-substituted dioxolane optionally substituted with chlorine atom Nylmethyl group, 2,2-diethoxyethyl group, 1-ethoxycarbonylethyl group, trimethylsilylmethyl group, 1-pyridylethyl group, lower alkoxyiminoalkyl group, or benzyloxyimino whose ring may be substituted with lower alkyl Which represents an alkyl group) or an acid addition salt thereof. 2. The following formula: (Wherein, R ₁ and R ₂ independently of each other represent a halogen atom or a lower alkyl group: X represents a leaving group), and a compound represented by the following formula: (In the formula, R ₃ represents a lower alkyl group or a cycloalkyl group having 3 to 5 carbon atoms; R ₄ represents a halogen atom or a lower alkyl group; n represents 0, 1 or 2, and Q represents 5 carbon atoms.
-10 alkyl group, allyl group, geranyl group, farnesyl group, lower alkyl group substituted with 1 to 4 halogen atoms, cycloalkyl-methyl group having 3 to 6 carbon atoms, lower alkoxyalkyl group, lower alkoxyalkoxy Alkyl group, lower alkylthioethyl group, lower alkylsulfonylethyl group, phenoxyethyl group substituted with 1 or 2 lower alkyl, glycidyl group, acetonyl group, dioxolanylmethyl group, optionally substituted with chlorine atom Phenoxymethyl-substituted dioxolanylmethyl group, 2,2-diethoxyethyl group, 1-ethoxycarbonylethyl group, trimethylsilylmethyl group, 1
A pyridylethyl group, a lower alkoxyiminoalkyl group, or a benzyloxyiminoalkyl group whose ring may be substituted with lower alkyl). The following formula: (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , n and Q have the same meanings as defined above.) A method for producing a compound or an acid addition salt thereof. 3. The following formula: (In the formula, R ₁ and R ₂ each 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; and R ₄ represents a halogen atom or a lower alkyl. Represents a group; n represents 0, 1 or 2; Q represents 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, carbon Cycloalkyl-methyl group, lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, lower alkylthioethyl group, lower alkylsulfonylethyl group, phenoxyethyl group substituted with 1 or 2 lower alkyl groups, and glycidyl group , Acetonyl group, dioxolanylmethyl group, phenoxymethyl-substituted dioxolane optionally substituted with chlorine atom Nylmethyl group, 2,2-diethoxyethyl group, 1-ethoxycarbonylethyl group, trimethylsilylmethyl group, 1-pyridylethyl group, lower alkoxyiminoalkyl group, or benzyloxyimino whose ring may be substituted with lower alkyl An insecticide, which comprises a compound represented by the formula (1) or an acid addition salt thereof as an active ingredient. 4. The following formula: (In the formula, R ₁ and R ₂ each 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; and R ₄ represents a halogen atom or a lower alkyl. Represents a group; n represents 0, 1 or 2; Q represents 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, carbon Cycloalkyl-methyl group, lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, lower alkylthioethyl group, lower alkylsulfonylethyl group, phenoxyethyl group substituted with 1 or 2 lower alkyl groups, and glycidyl group , Acetonyl group, dioxolanylmethyl group, phenoxymethyl-substituted dioxolane optionally substituted with chlorine atom Nylmethyl group, 2,2-diethoxyethyl group, 1-ethoxycarbonylethyl group, trimethylsilylmethyl group, 1-pyridylethyl group, lower alkoxyiminoalkyl group, or benzyloxyimino whose ring may be substituted with lower alkyl Represents an alkyl group) or an acid addition salt thereof as an active ingredient. 5. The following formula: (In the formula, R ₁ and R ₂ each 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; and R ₄ represents a halogen atom or a lower alkyl. Represents a group; n represents 0, 1 or 2; Q represents 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, carbon Cycloalkyl-methyl group, lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, lower alkylthioethyl group, lower alkylsulfonylethyl group, phenoxyethyl group substituted with 1 or 2 lower alkyl groups, and glycidyl group , Acetonyl group, dioxolanylmethyl group, phenoxymethyl-substituted dioxolane optionally substituted with chlorine atom Nylmethyl group, 2,2-diethoxyethyl group, 1-ethoxycarbonylethyl group, trimethylsilylmethyl group, 1-pyridylethyl group, lower alkoxyiminoalkyl group, or benzyloxyimino whose ring may be substituted with lower alkyl Which represents an alkyl group) or an acid addition salt thereof as an active ingredient.