JPH0539271A - Pyrimidine derivative, its production and germicidal, insecticidal and miticidal agent containing the same derivative as active component - Google Patents

Abstract

PURPOSE:To provide new compounds useful as a germicidal, insecticidal and miticidal agent. CONSTITUTION:Compounds of formula I (R1 is lower alkyl; R2 is lower alkyl or halogen; R1 and R2 together, form trimethylene or tetramethylene; R3 is H, lower alkyl or halogen; R4 is H or lower alkyl; R5 is H, lower alkyl or methylthio; (n) is 2 or 3), e.g. 4-[2-(4-benzylphenoxy)ethylamino]-5,6- tetramethylenepyrimidine. The compounds of formula I can be obtained by reacting a halopyrimidine derivative of formula II (Y is halogen) with an amine derivative of formula III, as necessary, in the presence of a base (e.g. triethylamine) in a solvent (e.g. chloroform) at room temperature to 250 deg.C. Excellent effects are shown to plant disease injuries such as rice blast, tomato late blight and grape downy mildew and brown planthoppers, houseflies, diamondback moths, Tetranychus urticae koch, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a pyrimidine derivative, a method for producing the same, and a bactericidal, insecticidal and acaricidal agent containing the pyrimidine derivative as an active ingredient.

[0002]

2. Description of the Related Art It is disclosed in JP-A-63-156781 and JP-A-55-76804 that certain pyrimidine derivatives exhibit bactericidal activity, insecticidal activity and acaricidal activity.

[0003]

However, the activity of these compounds as fungicides, insecticides and acaricides cannot always be said to be satisfactory.

[0004]

Means for Solving the Problems The inventors of the present invention have made diligent studies in consideration of such a situation. As a result, the pyrimidine derivative represented by the following general formula 4 shows excellent bactericidal, insecticidal and acaricidal activity. The inventors have found out that, and have reached the present invention. That is, the present invention has the general formula

[0005]

[Chemical 4]

[In the formula, R ₁ represents a lower alkyl group,
R ₂ represents a lower alkyl group or a halogen atom,
Alternatively, R ₁ and R ₂ are joined at the ends to represent a trimethylene group or a tetramethylene group. R ₃ represents a hydrogen atom, a lower alkyl group or a halogen atom, R ₄ represents a hydrogen atom or a lower alkyl group, R ₅ represents a hydrogen atom,
It represents a lower alkyl group or a methylthio group, and n represents 2 or 3. ] A pyrimidine derivative represented by the following (hereinafter referred to as the compound of the present invention), a method for producing the same, and a bactericidal, insecticidal, and acaricidal agent containing the same as an active ingredient. In the general formula 4, the lower alkyl group has 1 to 4 carbon atoms.
Represents an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The following can be said with respect to the compound of the present invention represented by the general formula 4 from the viewpoint of bactericidal activity, insecticidal activity, acaricidal activity and the like. R ₁ represents an ethyl group, and
R ₂ represents an ethyl group, a chlorine atom or a bromine atom,
Alternatively, a compound in which R ₁ and R ₂ are bonded to each other at the terminal to represent a trimethylene group or a tetramethylene group is preferable. Among these, from the viewpoints of bactericidal activity and phytotoxicity to plants, a compound in which R ₁ and R ₂ are bonded to each other at the terminal to represent a tetramethylene group or a trimethylene group is particularly preferable, and next, R ₁ and R ₂ are ethyl groups. The compounds represented are preferred, followed by the compounds in which R ₁ represents an ethyl group and R ₂ represents a chlorine atom. From the viewpoint of acaricidal activity, R ₁ represents an ethyl group, and particularly preferred compounds wherein R ₂ represents a chlorine atom, then the compound R ₁ and R ₂ represents an ethyl group are preferred, the following Further, a compound in which R ₁ and R ₂ are bonded at the terminal to represent a tetramethylene group or a trimethylene group is preferable. R ₃ , R ₄ and R
₅ represents a hydrogen atom, R ₃ and R ₄ represent a hydrogen atom, and R ₅ represents a methyl group or a methylthio group, R ₃ represents a methyl group, and R ₄ and R _4
5 represent a hydrogen atom, or, R ₃ and R ₄ represents a methyl group, and a compound wherein R ₅ represents a hydrogen atom or a methyl group is preferable. Of these, compounds in which R ₃ represents a methyl group and R ₄ and R ₅ represent hydrogen atoms are particularly preferred, and R ₃ and R ₄ represent a methyl group from the viewpoint of acaricidal activity, and Compounds in which R ₅ represents a hydrogen atom or a methyl group are also particularly preferred. n
Is preferably a compound representing 2.

The compound of the present invention is effective against various plant diseases.
It shows a controlling effect in terms of preventive effect, therapeutic effect, and permeation transfer effect. The plant diseases which the compound of the present invention has a controlling effect include rice blast (Pyricularia oryzae) , sesame leaf blight (Cochliobolus miyabeanus) , and blight (Rhizoctoni ) .
a solani) , powdery mildew of wheat (Erysiphe graminis,
f .SP . hordei, f.SP. tritici) , Fusarium head blight (Gibberel)
la zeae) , rust (Puccinia striiformis, P.gramin
is, P. recodita, P. hordei) , snow rot (Typhhula s
p., Micronectriella nivalis) , naked smut (Ustilago
tritici, U. nuda) , lintel smut (Tilletia cari
es) , eyeblight (Pseudocercosporella herpotrichoides
) , Cloud disease (Rhynchosporium secalis) , leaf blight (Sep
toria tritici) , wilt disease (Leptosphaeria nodorum)
) , Citrus black spot (Diaporthe citri) , scab (Elsinoe fawcetti) , fruit rot (Penicillium di)
gitatum, P. italicum) , monili disease of apple (Sclerot
inica mail) , rot (Valsa mail) , powdery mildew
(Podpsphaera leucotricha) , leaf spot disease (Alternar)
iamail) , scab (Venturia inaequalis) , pear scab (Venturia nashicola, V. pirina) , black spot
(Alternaria kikuchiana) , scab (Gymnosporangiu )
m haraeanum) , Peach scab (Sclerotinia cinerea)
) , Scab (Cladosporium carpophilum) , rot Phomopsis (Phomopsis sp.) , Black rot of grape (El
sinoe ampelina) , late rot (Glomerella cingulata) ,
Powdery mildew (Uncinula necator) , rust (Phakopsora )
ampelopsidis) , black lot disease (Guignardia bid)
wellii) , downy mildew (Plasmopara viticola) , anthracnose of oyster (Gloeosporium kaki) , leaf blight (Cercospora ka)
ki, Mycosphaerella nawae) , anthracnose of cucumber (Collet
otrichum lagenarium) , powdery mildew (Sphaerotheca f
uliginea) , vine blight (Mycosphaerella melonis) , downy mildew (Pseudoperonospora cubensis) , plague (Phytopht )
hora sp.) , tomato ring spot (Alternaria solani) ,
Leaf mold (Cladosporium fulvum) , plague (Phytophtho )
ra infestans) , eggplant brown leaf blight (Phomopsis vexans) ,
Powdery mildew (Erysiphe cichoracearum) , Black spot of cruciferous vegetables (Alternaia japonica) , White spot (Cercospo )
rella brassicae) , rust onion (Puccinia alli)
i), soybean purpura (Cercospora kikuchii), sphaceloma disease (Elsinoe glycines), black spot disease (Diaporthe phaseo
lorum var.sojae) , kidney anthracnose (Colletotric)
hum lindemthianum) , peanut black scab (Mycosphae)
rella personatum) , brown spot (Cercospora arachidico)
la) , powdery mildew of pea (Erysiphe pisi) , summer blight of potato (Alternariasolani) , plague (Phyto )
phthora infestans) , strawberry powdery mildew (Sphaeroth)
eca humuli) , tea leaf blast (Exobasidium reticul)
atum) , white scab (Elsinoe leucospila) , tobacco scab (Alternaria longipes) , powdery mildew (Erysiphe )
cichoracearum) , anthracnose (Colletotrichum tabacum
) , Downy mildew (Peronospora tabacina) , plague (Phytoph )
thoranicotianae) , brown leaf spot of sugar beet (Cercospora b)
eticola) , rose scab (Diplocarpon rosae) , powdery mildew (Sphaerotheca pannosa) , brown spot of chrysanthemum (Se)
ptoria chrysanthemi -indici) , white rust (Puccinia)
horiana) , gray mold of various crops ( Botrytis ciner
ea) , sclerotinia sclerotiorum, etc. Among these, the compound of the present invention is particularly effective for downy mildew and epidemics of various crops.

Examples of pests and harmful mites for which the compound of the present invention is effective include the following. Hemiptera Pests Planthoppers such as the brown planthopper, the brown planthopper, and the white-bellied planthopper, leafhoppers such as leafhoppers, leafhoppers such as the Taiwanese leafhopper leafhoppers, aphids, stink bugs, whiteflies, scale insects, leaf bugs, insects and insects, scale bugs , Plutella xylostella, etc., Spodoptera litura, Spodoptera litura, Spodoptera litura, etc.
Hamoguriga acids, tussock acids, Uwaba acids, Kaburayaga, Agurotisu genus pests such as black cutworm (Agrothis spp.), Heliothis spp pest (Heliothis spp.), Plutella xylostella, clothes moth, webbing clothes moth, etc. Diptera Culex, Culex such as Culex, Aedes mosquitoes such as Aedes aegypti and Aedes albopictus, Anopheles mosquitoes such as Aedes albopictus, chironomids, house flies, house flies such as house flies, blow flies, flesh flies, house flies, fruit flies, fruit flies, fruit flies, fruit flies such as onion fly , Coleoptera, flies, sand flies, etc. Coleoptera insect pests Western corn rootworm, southern corn rootworm, etc. corn rootworms, chafer beetles such as stag beetle, stag beetle, weevils such as weevils, weevils, chai Rice Roh mealworm, mealworm such as red flour beetle, Kisujinomihamushi, beetle such as corn rootworm, beetles such, Henosuepirakuna genera such as the beetle, Epilachna vigintioctopunctata (Henosu
epilacha spp.), flat beetle, long-tailed beetle, long-horned beetle, long-tailed beetle, blue-footed stag beetle, etc. Eye pests Ants, wasps, wasps, wasps and other wasps, etc.Orthoptera pests Kerala, grasshoppers, etc.Heptoptera pests, human flea, etc.Lice pests Human lice, lice etc., pests, etc. It is effective against ticks, ticks, citrus mites, citrus mites, apple spider mites, etc. Ticks Ocho ticks, house dust mites, mites, dust mites, tick mites, house dust mites, etc. Of these, the compounds of the present invention are particularly effective against spider mites. Next, the method for producing the compound of the present invention will be described in detail. The compound of the present invention has the general formula

[0009]

[Chemical 5]

[In the formula, R ₁ , R ₂ and Y have the same meanings as described above. ] And a halopyrimidine derivative represented by the general formula:

[0011]

[Chemical 6]

[Wherein R ₃ , R ₄ , R ₅ and n have the same meanings as described above. ] The amine derivative represented by the above can be produced by reacting in the presence of a base, if necessary. In the above reaction, the reaction temperature range is usually from room temperature to about 250 ° C, preferably 50 ° C to 2 ° C.
The reaction time is about 10 minutes to about 12 hours. The amount of reagents used in the reaction is represented by the general formula
The amount of the amine derivative represented by the general formula 6 is 1 to 5 moles, more preferably 1 to 2 moles, relative to 1 mole of the halopyrimidine derivative represented by.
Moles can also be used. Examples of the base used include alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates such as sodium carbonate, triethylamine, N,
Examples thereof include organic bases such as N-diethylaniline, pyridine, diazabicycloundecene, and the like, or a mixture thereof. The amine derivative represented by the general formula 6 can be used as a base itself. In the above reaction, a reaction solvent is not always necessary, but it is generally carried out in the presence of a solvent. Solvents that can be used include aromatic hydrocarbons such as benzene and toluene, halogenated aromatic hydrocarbons such as chlorobenzene, aliphatic hydrocarbons such as hexane and cyclohexane, halogens such as chloroform, dichloromethane and dichloroethane. Modified aliphatic hydrocarbons, ketones such as acetone, methyl ethyl ketone, cyclohexanone, esters such as ethyl acetate,
Diethyl ether, tetrahydrofuran, dioxane,
Ethers such as ethylene glycol dimethyl ether,
Alcohols such as methanol and ethanol, water, N, N
-Dimethylformamide, pyridine and the like or any mixture thereof. After completion of the reaction, the reaction solution is subjected to usual post-treatment such as extraction and concentration under reduced pressure, and if necessary,
The compound of the present invention can be obtained by purification operations such as chromatography and recrystallization. Examples of the compound of the present invention that can be produced according to the above production method are shown in Tables 1 to 15.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

[Table 4]

[0017]

[Table 5]

[0018]

[Table 6]

[0019]

[Table 7]

[0020]

[Table 8]

[0021]

[Table 9]

[0022]

[Table 10]

[0023]

[Table 11]

[0024]

[Table 12]

[0025]

[Table 13]

[0026]

[Table 14]

[0027]

[Table 15]

The halopyrimidine derivative represented by the general formula (5), which is one of the starting compounds for producing the compound of the present invention, is described in a known method, for example, JP-A-63-156781 and JP-A-58-222070. It can be easily synthesized by the method described above. In addition, the amine derivative represented by the general formula (6), which is the other starting compound for producing the compound of the present invention, can be prepared by, for example, the reaction formula (7).

[0029]

[Chemical 7]

It can be manufactured according to In the reaction formula 7, the chemical formulas 8 to 16 are

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical formula 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[In the formula, R ₃ , R ₄ , R ₅ and n have the same meanings as described above, and X represents a halogen atom. ]] Is represented. In the reaction formula 7, a compound in which R ₃ represents a chloro atom among the phenol derivatives represented by the general formula 13 which are synthetic intermediates of the amine derivative represented by the general formula

[0041]

[Chemical 17]

[In the formula, R ₄ and R ₅ have the same meanings as described above. ] It can also be manufactured according to. When the compound of the present invention is used as an active ingredient of a bactericide, it may be used as it is without adding any other component, but usually, it is mixed with a solid carrier, a liquid carrier, a surfactant and other formulation auxiliary agents. It is used by formulating into an emulsion, a wettable powder, a suspension, a powder, a granule and the like. In this case, the content of the active ingredient in the preparation of the compound of the present invention as the active ingredient is 0.1 to 99.9% by weight,
It is preferably 1 to 90%. As the above-mentioned solid carrier, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob flour, walnut flour, urea,
Examples of the liquid carrier include ammonium sulfate and fine powder or granules of synthetic hydrous silicon oxide, and the liquid carrier includes aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve.
Acetone, cyclohexenone, ketones such as isophorone,
Vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile, water and the like can be mentioned. Examples of surfactants used for emulsification, dispersion, and wet extension include alkyl sulfate ester salts, alkyl sulfonates, alkylaryl sulfonates, dialkylsulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts,
Anionic surfactants such as naphthalene sulfonic acid formalin condensates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. .. Examples of auxiliaries for the formulation include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP.
(Acid isopropyl phosphate) and the like. When the compound of the present invention is used as an active ingredient of a bactericide, the application amount of the active ingredient is usually 0.1 to 100 g, preferably 0.2 to 20 g per are, and emulsions, wettable powders, suspensions, etc. are treated with water. When diluted and applied, the application concentration is 0.00
The content is 01 to 0.5%, preferably 0.0005 to 0.2%, and powders and granules are applied as they are without any dilution. The compound of the present invention can also be used as a seed disinfectant,
It is expected to enhance the bactericidal efficacy by mixing with other bactericides. In addition, insecticides, acaricides, nematicides,
It can also be used as a mixture with a herbicide, a plant growth regulator or a fertilizer.

When the compound of the present invention is used as an active ingredient of insecticides and acaricides, it is usually mixed with a solid carrier, a liquid carrier, a gaseous carrier, a bait, or impregnated into a substrate such as a mosquito coil or mat. However, if necessary, surfactants and other auxiliaries for pharmaceuticals are added, and oils, emulsions, wettable powders, flowable agents such as water suspensions and emulsions, granules, powders, aerosols, mosquitoes. Heating fumigants such as incense sticks, electric mosquito mats and no mats, self-burning fumigants / chemical reaction fumigants, heating fumigants such as porous ceramic plate fumes, fogging agents such as fogging, ULV Used as a drug, poison bait, etc. These formulations usually contain the compound of the present invention as an active ingredient in an amount of 0.001 to 95% by weight. Examples of solid carriers used for formulation include clays (kaolin clay,
Diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talc, ceramics, other inorganic minerals (serisite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulfate, phosphorus) Liquid, carrier, such as water, alcohols (methanol, ethanol, etc.), ketones (acetone, acetone, etc.).
Methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), Nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether,
Dioxane), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, vegetable oil such as cottonseed oil Examples of the gaseous carrier, that is, the propellant include CFC gas, butane gas, and LPG.
(Liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. can give. Examples of formulation auxiliary agents such as sticking agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol). , Polyvinylpyrrolidone, polyacrylic acids, etc., and examples of the stabilizer include PAP (isopropyl acid phosphate), BH
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , Surfactants, fatty acids or esters thereof, and the like. As a base material for poison baits, for example, cereal flour, vegetable oil, sugar, bait components of crystalline cellulose sugar, antioxidants such as dibutylhydroxytoluene, nordihydroguaiaretic acid, preservatives such as dehydroacetic acid,
Examples include food intake prevention materials such as red pepper powder, cheese flavors, and attractive flavors such as onion flavors. The formulation of a flowable agent (suspension in water or emulsion in water) is generally 1 to
75% compound to 0.5-15% dispersant, 0.1-10%
Suspension aid (for example, a protective colloid or a compound imparting thixotropy), 0 to 10% of a suitable auxiliary agent (for example, defoaming agent, rust preventive, stabilizer, spreading agent, penetration aid) , Antifreeze agents, antibacterial agents, antifungal agents, etc.) and finely dispersed in water. It is also possible to use an oil in which the compound is hardly dissolved in place of water to prepare a suspension in oil. As the protective colloid, for example, gelanin, casein, gums, cellulose ether, polyvinyl alcohol and the like are used. Examples of the compound that imparts thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid, and the like. The preparation thus obtained is used as it is or after diluted with water or the like. Further, it can be used simultaneously with or without being mixed with other insecticides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers and soil conditioners. When the compound of the present invention is used as an active ingredient of agricultural insecticides and acaricides, the application amount is usually 0.1 to 500 g per 10 ares, and when the emulsion, wettable powder, flowable agent, etc. are diluted with water and applied. , Its application concentration is 0.0001 to 1000ppm, and granules, powders, etc. are applied as they are without being diluted. When it is used as an active ingredient of a pesticidal insecticide or acaricide, 0.0001
Dilute to ~ 10,000ppm and apply, and apply as is for oils, aerosols, fumigants, fumigants, fumes, ULVs, poison baits, etc. The application amount and application concentration depend on the type of formulation, application time, application location, application method, type of pest, degree of damage, etc., and may be increased or decreased without regard to the above range. can do.

[0044]

EXAMPLES The compounds of the present invention will be described in more detail below with reference to Production Examples, Preparation Examples and Test Examples, but the present invention is not limited to these examples. First, a manufacturing example is shown. Production Example 1 4-chloro-5,6-tetramethylenepyrimidine 1.0 g
And 2- (4-benzylphenoxy) ethylamine 2.67 g
The mixture was heated and stirred at 150 ° C. for 1 hour. After cooling down,
50 ml of water was added to the reaction product, and extracted with 50 ml of chloroform three times. The oily residue obtained by drying over anhydrous magnesium sulfate and concentration under reduced pressure was subjected to silica gel column chromatography (elution solvent: hexane: acetone = 3: 1).
(V / v)) to obtain 0.8 g of 4- [2- (4-benzylphenoxy) ethylamino] -5,6-tetramethylenepyrimidine (the present compound (4)). Production Example 2 4,5-Dichloro-6-ethylpyrimidine 0.53 g and 2-
(4-benzyl-2-methylphenoxy) ethylamine
Dissolve 0.87 g in 3 ml of toluene and add 0.36 of triethylamine.
g was added and the mixture was heated under reflux for 2 hours. After allowing to cool, water 3
0 ml was added, and the mixture was extracted 3 times with 30 ml of chloroform. The oily residue obtained by drying over anhydrous magnesium sulfate and concentrating under reduced pressure was subjected to silica gel column chromatography (elution solvent hexane: acetone = 3: 1 (v / v)).
To give 4- [2- (4-benzyl-2-methylphenoxy) ethylamino] -5-chloro-6-ethylpyrimidine (the present compound (15)) (0.47 g). Production Example 3 4-chloro-5,6-tetramethylenepyrimidine 1.0 g
And 2- (4-benzyl-2-methylphenoxy) ethylamine (2.86 g) were reacted and treated in the same manner as in Production Example 1 to give 4- [2- (4-benzyl-2-methylphenoxy) ethylamino]. 0.75 g of -5,6-tetramethylenepyrimidine (the present compound (14)) was obtained. Production Example 4 A mixture of 1.0 g of 4-chloro-5,6 tetramethylenepyrimidine and 3.1 g of 2- (4-benzyl-2-chlorophenoxy) ethylamine was reacted and treated in the same manner as in Production Example 1 to give 4- [ 1.1 g of 2- (4-benzyl-2-chlorophenoxy) ethylamino] -5,6-tetramethylenepyrimidine (the present compound (7)) was obtained. Production Example 5 4,5-Dichloro-6-ethylpyrimidine 0.53 g and 2-
0.94 g of (4-benzyl-2,3-dimethylphenoxy) ethylamine was dissolved in 3 ml of toluene, reacted and treated in the same manner as in Production Example 2 to give 4- [2- (4-benzyl-2,3).
-Dimethylphenoxy) ethylamino] -5-chloro-
0.51 g of 6-ethylpyrimidine (the present compound (17))
Got The compounds of the present invention produced according to the above Production Examples are shown in Tables 16-18.

[0045]

[Table 16]

[0046]

[Table 17]

[0047]

[Table 18]

Next, production examples of starting compounds for producing the compound of the present invention will be shown. Reference Example 1 Preparation of 2- (4-benzylphenoxy) ethylamine a) 4-benzylphenol 18.4 g was dissolved in 100 ml of anhydrous tetrahydrofuran and cooled with ice under a nitrogen stream.
4.0 g of sodium hydride (60% oily) was added slowly. After stirring at room temperature for 1 hour, 12.0 g of bromoacetonitrile was added under ice cooling, and the mixture was heated under reflux for 3 hours. After allowing to cool, the reaction product was concentrated under reduced pressure, 100 ml of water was added to the residue, and the mixture was extracted twice with 100 ml of chloroform. After washing with water, drying over anhydrous magnesium sulfate and concentration under reduced pressure, the oily residue obtained was subjected to silica gel column chromatography (eluting solvent hexane: acetone = 3: 1 (v / v)),
19.1 g of (4-benzylphenoxy) acetonitrile was obtained. b) Lithium aluminum hydride (3.4 g) was suspended in anhydrous tetrahydrofuran (100 ml), and while cooling with ice under a nitrogen stream, (4-benzylphenoxy) acetonitrile (10.0 g).
Was gradually added. After stirring at room temperature for 1 hour, ice cooling again,
Carefully add 3.4 ml of water and then 3.4 ml of 5N aqueous sodium hydroxide to the reaction mixture, and finally add 10 ml of water,
Stir for a while. Unnecessary substances were filtered off using Celite, and the filtrate was concentrated under reduced pressure to obtain 9.8 g of 2- (4-benzylphenoxy) ethylamine. This product was used for the next reaction without further purification. Reference Example 2 Preparation of 2- (4-benzyl-2-methylphenoxy) ethylamine a) 12.15 g of ground magnesium and 50.23 g of 1-bromo-4-methoxy-3-methylbenzene to give anhydrous ether 2
The Grignard reagent was prepared in 00 ml according to a conventional method.
To this Grignard reagent, add 200 ml of anhydrous benzene,
The ether was distilled off under atmospheric pressure. To this solution, under heating under reflux,
A mixed solution of 47.25 g of benzyl bromide and 50 ml of anhydrous benzene was added dropwise, and the mixture was stirred for 3 hours. After allowing to cool, the reaction mixture was filtered, and the filtrate was washed successively with diluted hydrochloric acid, diluted caustic soda water, and water. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and then distilled under reduced pressure to obtain 30.8 g of 4-benzyl-2-methyl-1-methoxybenzene. b) 4-benzyl-2-methyl-1-methoxybenzene
A mixture of 30.8 g, hydrobromic acid 50 ml and acetic acid 100 ml was added to 5
Heated to reflux for a period of time. After allowing to cool, it was neutralized with an aqueous sodium hydrogen carbonate solution, and this was extracted twice with 100 ml of ethyl acetate. After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure, and the obtained oily residue was subjected to silica gel column chromatography (eluting solvent hexane: acetone =
3: 1 (v / v)) to obtain 23.7 g of 4-benzyl-2-methylphenol. c) 2- (4-Benzyl-2-methylphenoxy) ethylamine was produced from 4-benzyl-2-methylphenol in the same manner as in Reference Example 1. Reference Example 3 Preparation of 2- (4-benzyl-2-chlorophenoxy) ethylamine a) 4-benzylphenol 18.4 g was added to carbon tetrachloride 100
It was dissolved in ml and, under stirring, 10.85 g of t-butyl hypochlorite was added dropwise at -5 to 0 ° C. After stirring at room temperature for 3 hours, the reaction solution was washed with a saturated aqueous solution of sodium hydrogen carbonate and then with water. After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure, and the resulting oily residue was subjected to silica gel column chromatography (eluting solvent hexane: acetone = 3: 1).
(V / v)) to obtain 20.6 g of 4-benzyl-2-chlorophenol. b) 2- (4-benzyl-2-chlorophenoxy) ethylamine was produced in the same manner as in Reference Example 1 from 4-benzyl-2-chlorophenol.

Formulation examples are shown below. In addition, a part represents a weight part. Formulation Example 1 50 parts of each of the compounds (1) to (21) of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain each wettable powder. .. Formulation Example 2 25 parts of each of the compounds (1) to (21) of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed and wet until the particle size of the active ingredient is 5 microns or less. Grind to obtain each suspension. Formulation Example 3 2 parts of each of the compounds (1) to (21) of the present invention, Kaolin clay 8
8 parts and 10 parts of talc are well pulverized and mixed to obtain each powder. Formulation Example 4 20 parts of each of the compounds (1) to (21) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodenebenzenebenzenesulfonate, and 60 parts of xylene are mixed well to obtain each emulsion. .. Formulation Example 5 2 parts of each of the compounds (1) to (21) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed, and water is added. After thoroughly kneading, granulate and dry to obtain each granule. Formulation Example 6 10 parts of each of the compounds (1) to (21) of the present invention are dissolved in 35 parts of xylene and 35 parts of dimethylformamide, and 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added, Stir mix to obtain each 10% emulsion. Formulation Example 7 0.1 part of each of the compounds (1) to (21) of the present invention was dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this was deodorized kerosene 8
Mix with 9.9 parts to obtain each 0.1% oil solution. Formulation Example 8 0.1 parts of each of the present compounds (1) to (21), 0.2 parts of tetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorizing kerosene were mixed and dissolved, and the mixture was filled in an aerosol container, and the valve part was filled. After mounting, 30 parts of propellant (liquefied petroleum gas) is charged under pressure through the valve portion to obtain each oil-based aerosol. Next, it is shown in Test Examples that the compound of the present invention is useful as a bactericidal, insecticidal and acaricidal agent. The compounds of the present invention are shown by the compound numbers in Tables 16 to 18, and the compounds used for comparison and control are shown by the compound symbols in Table 19.

[0050]

[Table 19]

First, it is shown in Test Examples that the compounds of the present invention are useful as fungicides. In addition, the control efficacy is "5", 10% if the disease state of the test plant at the time of the survey, that is, the flora of leaves, stems, etc. If the degree is recognized, "4", if about 30% is recognized, "3", if about 50% is recognized, "2",
If about 70% is recognized, it is evaluated as “1”, and if it is not more than that, the condition is not evaluated.
Shown as 2,1,0. Test Example 1 Tomato epidemic control test (preventive effect) A plastic pot was filled with sandy loam soil, seeded with tomato (ponterosa), and grown in a greenhouse for 20 days. 2 true leaves
Tomato seedlings spread on about one sheet were diluted with water to obtain a test compound, which was made into a wettable powder according to Formulation Example 1, to a predetermined concentration, and the foliage was sprayed so that it was sufficiently attached to the leaf surface. After spraying, a zoosporangium suspension of Phytophthora infestans was spray-inoculated. 23 ° C after inoculation
After keeping it under high humidity overnight, grow it in the greenhouse for 4 days,
The control efficacy was investigated. The results are shown in Table 20.

[0052]

[Table 20]

Test Example 2 Grapes and Disease Control Test (Preventive Effect) A plastic pot was filled with sandy loam soil, seeded with grape (berry A), and grown in a greenhouse for 40 days. A test compound prepared as a suspending agent according to Formulation Example 2 was diluted with water to a seedling of grape having three or more true leaves developed to give a predetermined concentration, and the compound was sprayed on foliage so as to sufficiently adhere to the leaf surface. After spraying, a suspension of zoosporangium of grapevine and disease fungus was spray-inoculated. 23 after inoculation
After left overnight at high temperature and high humidity, it was further grown in a greenhouse for 7 days, and the control efficacy was investigated. The results are shown in Table 21.

[0054]

[Table 21]

Test Example 3 Tomato Epidemic Control Test (Therapeutic Effect) A plastic pot was filled with sandy loam soil, and tomatoes (Ponterosa) were sown and grown in a greenhouse for 20 days. 2 true leaves
The tomato seedlings that had spread to about one piece were spray-inoculated with a zoosporangium suspension of Phytophthora infestans. After inoculation, the mixture was left overnight under high humidity at 23 ° C., and then the test compound, which was made into a suspension according to Formulation Example 2, was diluted with water to a predetermined concentration, and the foliage was sprayed so that it adhered sufficiently to the leaf surface. .. After spraying, grow for 4 days in the greenhouse,
The control efficacy was investigated. The results are shown in Table 22.

[0056]

[Table 22]

Next, it will be shown by test examples that the compound of the present invention is useful as an active ingredient of insecticides and acaricides. Test Example 4 Insecticidal test against Culex pipiens In accordance with Formulation Example 6, the test compound was made into an emulsion, which was then diluted with water.
It was diluted 8500 times, and then 0.7 ml was added to 100 ml of ion-exchanged water (concentration of active ingredient: 3.5 ppm). Twenty larvae of the Culex pipiens larvae were released therein, and then fed and fed for about 8 days until all untreated plots emerged, and the inhibition rate of emergence was examined. The effect evaluation standard was (eclosion inhibition rate) a: 90% or more, b: 80% or more and less than 90%, and c: less than 80%. The results are shown in Table 23.

[0058]

[Table 23]

Test Example 5 Insecticidal test against housefly A filter paper of the same size is laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, the test compound is made into an emulsion according to Preparation Example 6, and a 200-fold diluted solution (500 ppm) 0.7 with water is prepared. ml was dropped on a filter paper, and 30 mg of sucrose was uniformly added as a bait. Ten adult housefly females were released therein, the lid was put on, 48 hours later, the life and death thereof were investigated, and the mortality rate was calculated (2 repetitions). The results are shown in Table 24.

[0060]

[Table 24]

Test Example 6 Insecticidal test against larvae of the brown planthopper, an emulsion of the test compound obtained according to Formulation Example 6 was diluted with water (500 ppm) to give 1 rice stem (length: about 12 cm).
Soaked for a minute. After air-drying, rice stalks were placed in a test tube, and about 30 larvae of the brown planthopper were released therein, and after 6 days, their life and death were investigated to determine the mortality rate. The criteria are: a: No live insects are found. b: Five or less surviving insects are recognized. c: Six or more live insects are recognized. And The results are shown in Table 25.

[0062]

[Table 25]

Test Example 7 Insecticidal test against Southern corn rootworm A polyethylene cup having a diameter of 5.5 cm was covered with a filter paper of the same size, and an emulsion of the test compound obtained according to Formulation Example 6 was diluted with water ( 50 ppm) 1 ml was dropped on the filter paper, and one corn sprouting was put in as a bait. Approximately 30 eggs of Southern corn rootworm were placed therein, the lid was put on, and 8 days later, the life and death of hatched larvae were examined to determine the mortality rate. The criteria for effect evaluation are: a: No live insects are observed. b: Five or less surviving insects are recognized. c: Six or more live insects are recognized. And The results are shown in Table 26.

[0064]

[Table 26]

Test Example 8 Ovicidal test against diamondback moth A radish sprouting with eggs adhering within 6 hours after birth in a diluted solution (50 ppm) of water of the emulsion of the test compound obtained according to Formulation Example 6 ( Two seedlings were soaked for 30 seconds 5 to 6 days after seeding. After air-drying, two sprouting were placed in a polyethylene cup having a diameter of 5.5 cm, and the life and death of the bud were examined 6 days later. The mortality rate was divided into the following three levels and displayed. a: 100% b: 70% or more and less than 100% c: less than 70% The results are shown in Table 27.

[0066]

[Table 27]

Test Example 9 Test Against Red Mite (Pseudomonas aeruginosa) On day 7 of sowing, potted vines (green leaves) (primary leaf stage) were infested with 10 adult females of the Japanese red mite, Periphyton communis,
It was placed in a constant temperature room at 25 ° C. Six days later, the test compound was made into an emulsion according to Formulation Example 6, and 15 ml per pot of the drug solution diluted with water to 500 ppm of the active ingredient was sprayed on the turntable, and 2 ml of the same solution was simultaneously irrigated with soil. After 8 days, the degree of damage caused by the mites on each plant was investigated. The criteria for effectiveness are: -No damage is observed. +: Some damage is recognized. ++: The same damage as in the untreated area is recognized. And The results are shown in Table 28.

[0068]

[Table 28]

Test Example 10 Test against Nymphalid mites Each emulsion of the test compound obtained according to Formulation Example 6 was diluted with water to a predetermined concentration to obtain a diluted solution. Prepare 2 pots of potted vine bean beans infested with spider mites, sprinkle 40 ml of the diluted solution, and 2 ml per pot at the same time
Was soil-irrigated. The number of female adults before the treatment, 11 days after the treatment, and 15 days after the treatment was examined, and the control value was calculated from the following formula. The results are shown in Tables 29 and 30.

[0070]

[Table 29]

[0071]

[Table 30]

[0072]

Since the compound of the present invention has excellent effects on various plant diseases, insects and mites, it can be used for various purposes as an active ingredient for bactericidal, insecticidal and acaricidal agents.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Kishida 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd.

Claims (3)

[Claims] 1. A general formula: ## STR1 ## [Wherein R ₁ represents a lower alkyl group, R ₂ represents a lower alkyl group or a halogen atom, or
₁ and R ₂ are combined at the terminal to represent a trimethylene group or a tetramethylene group. R ₃ represents a hydrogen atom, a lower alkyl group or a halogen atom, R ₄ represents a hydrogen atom or a lower alkyl group, R ₅ represents a hydrogen atom, a lower alkyl group or a methylthio group, and n represents 2 or 3. ] The pyrimidine derivative shown by these. 2. A general formula: ## STR2 ## [Wherein R ₁ represents a lower alkyl group, R ₂ represents a lower alkyl group or a halogen atom, or
₁ and R ₂ are combined at the terminal to represent a trimethylene group or a tetramethylene group. Y represents a halogen atom. ] And a halopyrimidine derivative represented by the general formula: [Wherein R ₃ represents a hydrogen atom, a lower alkyl group or a halogen atom, R ₄ represents a hydrogen atom or a lower alkyl group, R ₅ represents a hydrogen atom, a lower alkyl group or a methylthio group, and n is 2 or Represents 3. ] The amine derivative shown by these is made to react, The manufacturing method of the pyrimidine derivative of Claim 1 characterized by the above-mentioned. 3. A bactericidal, insecticidal and acaricidal agent comprising the pyrimidine derivative according to claim 1 as an active ingredient.