JP2003155204A - Insecticide comprising triazine compound as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an insecticide having excellent efficacy. SOLUTION: This insecticide comprises a 1,3,5-triazine compound represented by formula (1) [R<1> a 3-7C alkynyl group which may be substituted with a halogen atom; R<2> is a halogen atom, a 1-4C alkyl group, a 1-3C haloalkyl group, a 1-4C alkoxy group, a 1-4C haloalkoxy group, a cyano group or a nitro group; n is an integer of 0-5; when n is an integer of >=2, R<2> s may be the same or different; A is a single bond, a CR<3> R<4> group, an oxygen atom, a sulfur atom or an NR<5> group; R<3> and R<4> are each independently a hydrogen atom or a 1-4C alkyl group; R<5> is a 1-4C alkyl group or a hydrogen atom] as an active ingredient. This method for controlling insect pests comprises applying the effective amount of the 1,3,5-triazine compound represented by formula (1) to insect pests or an insect pest habitat.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an insecticide containing a 1,3,5-triazine compound as an active ingredient.

[0002]

BACKGROUND OF THE INVENTION Since pests harm agricultural crops, various chemical agents have been developed and put to practical use for their control, but their efficacy is not always sufficient. is there. Therefore, in these fields, the development of new drugs having excellent efficacy is desired. An object of the present invention is to provide an insecticide having excellent efficacy.

[0003]

Means for Solving the Problems As a result of intensive studies to find an insecticide having excellent efficacy, the present inventor has found that a 1,3,5-triazine compound represented by the following formula (1) has an excellent insecticidal activity. The present invention has been completed by finding out that
That is, the present invention relates to formula (1) and formula (1) [Wherein R ¹ is C optionally substituted by a halogen atom]
Represents a 3-C7 alkynyl group, R ² is a halogen atom, C
1-C4 alkyl group, C1-C3 haloalkyl group, C1
It represents a -C4 alkoxy group, a C1-C4 haloalkoxy group, a cyano group or a nitro group, and n represents an integer of 0-5.
However, when n represents an integer of 2 or more, R ² may be the same or different. A represents a single bond, a CR ³ R ⁴ group, an oxygen atom, a sulfur atom or an NR ⁵ group. R ³ and R ⁴ each independently represent a hydrogen atom or a C1-C4 alkyl group, and R ⁵ represents a C1-C4 alkyl group or a hydrogen atom. ] The pesticide characterized by containing the 1,3,5-triazine compound shown by these as an active ingredient (it is hereafter described as the pesticide of this invention.), And 1,3 shown by Formula (1).
Provided is a pest control method, which comprises applying an effective amount of a 5-triazine compound to a pest or a habitat of the pest.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION First, a 1,3,5-triazine compound represented by the formula (1) (hereinafter referred to as the present compound), which is an active ingredient of the insecticide of the present invention, will be described.

In the present compound, examples of the C3-C7 alkynyl group which may be substituted with a halogen atom represented by R ¹ include 2-propynyl group and 1-methyl-2-
Examples include propynyl group, 2-butynyl group, 1-methyl-2-butynyl group, 2-pentynyl group, 4-methyl-2-pentynyl group, 3-chloro-2-propynyl group and 3-iodo-2-propynyl group. To be

Examples of the halogen atom represented by R ² include fluorine atom, chlorine atom and bromine atom, and C
Examples of the 1-C4 alkyl group include a methyl group, an ethyl group, an isopropyl group and a 1,1-dimethylethyl group, and examples of the C1-C3 haloalkyl group include a trifluoromethyl group and a difluoromethyl group, Examples of the C1-C4 alkoxy group include a methoxy group and an ethoxy group, and examples of the C1-C4 haloalkoxy group include a difluoromethoxy group, a trifluoromethoxy group and a 1,1,2,2-tetrafluoroethoxy group. can give.

Examples of the CR ³ R ⁴ group represented by A include a CH ₂ group, a CH (CH ₃ ) group and a CH (C ₂ H ₅ ) group, and examples of the NR ⁵ group include an NH group and an NCH group. Examples include ₃ groups and NC ₂ H ₅ groups.

As the embodiment of the present compound, for example, a compound of the general formula (1) in which R ¹ is a 2-butynyl group; a compound of the general formula (1) in which R ¹ is a 2-pentynyl group, a general formula (1) In the general formula (1), R ¹ is a 2-butynyl group and A is a single bond; in the general formula (1), R ¹ is a 2-pentynyl group and A is A compound which is a single bond; a compound in which R ² is a halogen atom or a C1-C4 alkyl group in the general formula (1), and n is an integer of 0 to 2; R ¹ in the general formula (1) is a 2-butynyl group Wherein A is a single bond, R ² is a halogen atom or a C1-C4 alkyl group, and n is an integer of 0 to 2; R ¹ is a 2-pentynyl group in the general formula (1). Yes, A is a single bond, R ² is a halogen atom And a C1-C4 alkyl group, and n is an integer of 0 to 2.

Next, a method for producing the present compound will be described.
The present compound is, for example, the following (I) to
It can be produced by the method shown in (III). (I)
Among the compounds represented by the formula (1), A is a single bond or CR ³ R
^The compound of formula ⁴ is a compound of formula (2) and a compound of formula R ¹ OH
It can be produced by reacting with an alcohol compound represented by (In the formula, R ¹ , R ² and n have the same meanings as described above, and A ¹
Represents a single bond or CR ³ R ⁴ . ) The reaction is usually performed in a solvent. Examples of the solvent used in the reaction include ethers such as tetrahydrofuran,
Examples include acid amides such as N, N-dimethylformamide, aromatic hydrocarbons such as toluene, and mixtures thereof. Examples of the base used in the reaction include inorganic bases such as sodium hydride. The amount of the base used in the reaction is based on 1 mol of the compound represented by the formula (2).
It is usually in the range of 1 to 1.2 mol. R used in the reaction
The amount of the alcohol compound represented by ¹ OH is usually 1 to 1.2 mol per 1 mol of the compound represented by the formula (2). The reaction temperature is usually in the range of 0 to 50 ° C, and the reaction time is usually in the range of 1 to 24 hours. The reaction mixture after completion of the reaction can be subjected to post-treatment operations such as extraction with an organic solvent, drying and concentration of the organic layer to isolate the compound of the present invention represented by the general formula (1-1), If necessary, it can be further purified by recrystallization, chromatography or the like.

(II) Of the compounds represented by the formula (1), those in which A is a single bond or CR ³ R ⁴ are prepared by reacting the compound represented by the formula (3) with a salt of formamidine in the presence of a base. It can be manufactured by (In the formula, R ¹ , R ² , n and A ¹ have the same meanings as described above, and R ⁶ represents a methyl group or an ethyl group.) The reaction is usually performed in a solvent. Examples of the solvent used in the reaction include alcohols such as ethanol and 2-propanol, ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether, and N, N.
-Acid amides such as dimethylformamide, aromatic hydrocarbons such as toluene, sulfoxides such as dimethyl sulfoxide, and mixtures thereof. Examples of the base used in the reaction include tertiary amines such as triethylamine. The amount of base used in the reaction is
Generally, 1 mol is used for 1 mol of the compound represented by the general formula (3).
It is a ratio of 10 mol. Examples of the salt of formamidine used in the reaction include inorganic salts such as hydrochloride. The amount of the formamidine salt used in the reaction is usually 1 to 2 with respect to 1 mol of the compound represented by the general formula (3).
It is a molar ratio. The reaction temperature is usually in the range of 20 to 100 ° C., and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, water is added to the reaction mixture and the resulting solid is collected by filtration, or the reaction mixture is subjected to post-treatment operations such as extraction with an organic solvent, drying and concentration of the organic layer. The compound of the present invention represented by 1-1) can be isolated and, if necessary, further purified by recrystallization, chromatography and the like.

(III) Among the compounds represented by the formula (1), the compound in which A is an oxygen atom, a sulfur atom or an NR ⁵ group is a compound represented by the formula (4) and a compound represented by the formula (5). It can be produced by reacting in the presence of a base. (In the formula, R ¹ , R ² and n have the same meanings as described above, and
² represents an oxygen atom, a sulfur atom or an NR ⁵ group. The reaction is usually performed in a solvent, and examples of the solvent used in the reaction include ethers such as tetrahydrofuran,
Examples thereof include acid amides such as N, N-dimethylformamide, aromatic hydrocarbons such as toluene, sulfoxides such as dimethyl sulfoxide, and a mixture thereof. Examples of the base used in the reaction include inorganic bases such as potassium carbonate, sodium carbonate and sodium hydride. The amount of the base used in the reaction is usually 1 to 2 mol per 1 mol of the compound represented by the general formula (4). The amount of the compound represented by the formula (5) used in the reaction is usually 1 with respect to 1 mol of the compound represented by the formula (4).
˜1.2 mol. Reaction temperature is usually 20 to 10
It is in the range of 0 ° C., and the reaction time is usually in the range of 1 to 24 hours. The reaction solution after completion of the reaction can be subjected to post-treatment operations such as extraction with an organic solvent, drying and concentration of the organic layer to isolate the compound of the present invention represented by the formula (1-2). It can be further purified by recrystallization chromatography or the like depending on the case.

The compound represented by the general formula (2) includes the N-cyanoamidine compound represented by the general formula (6) and the compound represented by the formula (7).
It can be produced by reacting with an iminium salt represented by (In the formula, R ² , n and A ¹ have the same meanings as described above.) The reaction is usually performed in a solvent. Examples of the solvent used in the reaction include nitriles such as acetonitrile, halogenated hydrocarbons such as methylene chloride, ethers such as tetrahydrofuran, and mixtures thereof. The amount of the iminium salt represented by the formula (7) used in the reaction is usually 1 to 1.5 mol per 1 mol of the N-cyanoamidine compound represented by the formula (6). The reaction temperature is usually in the range of 0 to 50 ° C, and the reaction time is usually in the range of 1 to 24 hours. After completion of the reaction, water is added to the reaction mixture and the resulting solid is collected by filtration, or the reaction mixture is subjected to post-treatment operations such as extraction with an organic solvent and drying and concentration of the organic layer to obtain the desired product. Can be isolated and, if necessary, further purified by recrystallization, chromatography and the like.

The N-cyanoamidine compound represented by the formula (6) can be produced, for example, by reacting a salt of the amidine compound represented by the formula (8) with sodium hydrogen cyanamide. (In the formula, R ² and A ¹ have the same meanings as described above.) The reaction is usually performed in a solvent. Examples of the solvent used in the reaction include water. Examples of the salt of the amidine compound represented by the formula (8) include inorganic salts such as hydrochloride. Sodium hydrogencya used in the reaction
The amount of namide is the salt 1 of the amidine compound represented by the formula (8).
The amount is usually 1 to 1.2 mol per mol. The reaction temperature is usually in the range of 0 to 50 ° C, and the reaction time is usually in the range of 1 to 50 ° C.
The range is 24 hours. After completion of the reaction, the reaction solution can be isolated by adding water to collect the resulting solid, or by performing post-treatment operations such as extraction with an organic solvent and concentration. It can be further purified by recrystallization, chromatography or the like.

The compound represented by the general formula (3) is produced by reacting the N-acyl thiocarbamate compound represented by the general formula (9) with the compound represented by the general formula R ⁶ X in the presence of a base. can do. (In the formula, R ¹ , R ² n, R ⁶ and A ¹ have the same meanings as described above.) Examples of the compound represented by the formula R ⁶ X include methyl iodide and ethyl iodide. The reaction is usually performed in a solvent. Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, acid amides such as N, N-dimethylformamide, aromatic hydrocarbons such as toluene, and sulfoxides such as dimethylsulfoxide. And mixtures thereof, which are used properly according to the type of base used. The amount of the compound represented by the general formula R ⁶ X used in the reaction is usually 1 to 1.5 mol per 1 mol of the N-acylthiocarbamate compound represented by the general formula (9). Examples of the base used in the reaction include alkali metal alkoxides such as sodium methoxide and inorganic bases such as potassium carbonate and sodium hydride. The amount of the base used in the reaction is usually 1 to 1.5 mol per 1 mol of the N-acyl thiocarbamate compound represented by the general formula (9). Reaction temperature is usually -10
The reaction time is usually in the range of 1 to 24 hours. After the reaction is complete, water is added to the reaction mixture to collect the resulting solid, or the reaction mixture is extracted with an organic solvent, and the target product is isolated by performing post-treatment operations such as drying and concentration of the organic layer. If necessary, it can be further purified by recrystallization, chromatography or the like.

The N-acyl thiocarbamate compound represented by the general formula (9) is produced by reacting the acyl isothiocyanate compound represented by the general formula (10) with the alcohol compound represented by the general formula R ¹ OH. be able to. (In the formula, R ¹ , R ² , n and A ¹ have the same meanings as described above.) The reaction is usually carried out in a solvent, and examples of the solvent used in the reaction include halogenated carbon such as carbon tetrachloride. Hydrogen,
Aromatic hydrocarbons such as toluene and mixtures thereof may be mentioned. The amount of the alcohol compound represented by the formula R ¹ OH used in the reaction is usually 1 to 1.2 with respect to 1 mol of the acyl isothiocyanate compound represented by the formula (10).
It is a molar ratio. The reaction temperature is usually in the range of 20 to 80 ° C, and the reaction time is usually in the range of 1 to 24 hours. After completion of the reaction, the reaction mixture is subjected to a post-treatment operation such as extraction with an organic solvent, drying and concentration of the organic layer to isolate the desired product, or the residue obtained by concentrating the reaction mixture is used as a solvent. In some cases, the desired product can be isolated as crystals by cooling after dissolving in.

The acyl isothiocyanate compound represented by the general formula (10) can be produced, for example, by reacting the acid chloride compound represented by the general formula (11) with potassium thiocyanate or sodium thiocyanate. (In the formula, R ² , n and A ¹ have the same meanings as described above.) The reaction is usually carried out in a solvent, and examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene. . The amount of potassium thiocyanate or sodium thiocyanate used in the reaction is usually 1 to 1.5 mol per 1 mol of the acid chloride compound represented by the general formula (11). The reaction temperature is usually in the range of 20 to 120 ° C, and the reaction time is usually in the range of 1 to 24 hours. After completion of the reaction, the reaction mixture is filtered, and the desired product can be isolated by performing post-treatment operations such as concentration of the filtrate, and if necessary, it can be further purified by distillation or the like. The next step can be performed without performing any operation.

The compound represented by the formula (4) has the formula (11)
It can be produced by reacting 2,4-dichloro-1,3,5-triazine represented by and an alcohol compound represented by the formula R ¹ OH in the presence of a base. (In the formula, R ¹ has the same meaning as described above.) The reaction is usually performed in a solvent, and examples of the solvent used in the reaction include ethers such as tetrahydrofuran,
Examples thereof include acid amides such as N, N-dimethylformamide, aromatic hydrocarbons such as toluene, sulfoxides such as dimethyl sulfoxide, and a mixture thereof. Examples of the base used in the reaction include inorganic bases such as sodium hydride. The amount of the base used in the reaction is usually 1 to 1.2 mol relative to 1 mol of 2,4-dichloro-1,3,5-triazine represented by the formula (11). The amount of the alcohol compound represented by the formula R ¹ OH used in the reaction is usually 1 to 1: 1 with respect to 1 mol of 2,4-dichloro-1,3,5-triazine represented by the formula (11).
It is a ratio of 2 mol. The reaction temperature is usually in the range of -10 to 10 ° C, and the reaction time is usually in the range of 1 to 24 hours. The reaction mixture after completion of the reaction can be subjected to post-treatment operations such as extraction with an organic solvent, drying and concentration of the organic layer to isolate the desired product, and if necessary, recrystallization, chromatography, etc. It can be further purified.

Next, specific examples of this compound are shown in (Table 1) to (Table 3). Formula (1) The compound represented by.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

Examples of the pests which the insecticide of the present invention has a controlling effect on include the following insects. Hemiptera pests:
Great brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), sedge planthopper (Sogatell)
a furcifera) and other planthoppers, and leafhoppers (Nephot)
ettix cincticeps), Green leafhopper (Empoa)
leafhoppers such as scaonukii) and cotton aphids (Aphis go)
aphids such as ssypii) and green peach aphids (Myzus persicae), stink bugs, and whitefly whitefly (Trialeu
rodes vaporariorum), whitefly white tobacco (Bemisia ta
baci), silver leaf whitefly (Bemisia argentifo
whiteflies such as lii), scale insects, gum beetles, white lice, etc.

Lepidopteran pest: Nikameiga (Chilo suppress
alis), Kobunomeiga (Cnaphalocrocis medinalis), European corn borer (Ostrinia nubilalis), Shiga moths (Parapediasia teterrella), etc.
(Spodoptera exigua), armyworm (Pseudaletia sepa
rata), armyworm (Mamestra brassicae), tamanaga (A
grotis ipsilon), Trichoplusia s
pp.), Heliothis spp., Helicoverpa spp., Earias sp.
p.) and other moths, Pieris rapae cruci
Vora and other white butterflies, Adox
ophyes orana fasciata), Nasihime Shingui (Graphol
ita molesta), codling moss (Cydia pomonella), and other tortoises, and peach moth squid ((Carposina niponensi
s) etc., and peach moth (Lyonetia clerk)
ella, etc.
ringoniella) and other worms, citrus fruit moth (Phylloc
Nectar such as nistis citrella) and diamondback moth (Plutel
a xylostella), pink ball worm (Pecti
nophora gossypiella), etc., Hitriga, Hirosukoga, etc.

[0024] Diptera Pests: Culex pipiens
pallens), Culex tritaeniorhynchu
s), Culex quinquefasciatus, etc., (Aedes aegypti), (Aedes albopictus)
Genus Aedes, etc., (Anopheles sinensis) genus Anopheles, chironomids, housefly (Musca domestica),
Houseflies such as the housefly (Muscina stabulans),
Drosophila, flesh flies, sand flies, Delia platura, Delia antiqua and other fruit flies, fruit flies, fruit flies, butterfly flies, gnats, flies, sand flies, leaf flies, etc.

Coleoptera pests: Western corn rootworm (Diabrotica virgifera virgifera), Southern corn rootworm (Diabrotica undecimpunctata howardi)
Such as corn rootworm, Douganebubuibu (Anomal
a cuprea), Scarab beetle (Anomala rufocuprea), etc., Sitophilus zeamai
s), rice weevil (Lissorhoptrus oryzophilu)
s), Azuki bean weevil (Callosobruchuys chienensis)
Weevil, such as
brio molitor), Trifolium castan
eum) and other rice beetles, Oedem (Oulem)
a oryzae), corn rootworm (Aulacophora femoralis),
Chrysomelidae beetle (Phyllotreta striolata), Colorado potato beetle (Leptinotarsa decemlineata)
a vigintioctopunctata) and other epilacunas, flat beetles, long-tailed beetles, long-beaked beetles, blue-spotted beetles, Paederus fuscipes, etc .; Thrips pests: Thrips p
almi) and other thrips, such as Thrips palmi (Fran
kliniella occidentalis), etc., and Thrips thrips (Sciltothrips dorsalis, etc.) thrips, etc.

Hymenoptera pests: Habras, ants, wasps, etc., Lepidoptera pests: Cockroaches, German cockroaches, etc. Orthoptera pests: Grasshoppers, mosses, etc. Hideptera pests: Human flea and lice pests: Termite pests such as human lice: termites

The pesticide of the present invention may be the present compound itself, but usually, it is further mixed with a solid carrier, a liquid carrier, a gaseous carrier and / or a bait (poison bait base material), etc. It is formulated into oils, emulsions, flowables, granules, powders, poison baits, microcapsules, etc. by adding agents and other formulation auxiliary agents. These formulations include
The present compound is usually contained in an amount of 0.01 to 95% by weight.

Examples of the solid carrier used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talc, ceramics, and other inorganic minerals (sericite). , Quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.), etc. , Alcohols (methanol, ethanol, etc.), ketones (acetone, 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, iso Chironitoriru etc.), ethers (diisopropyl ether, dioxane, etc.),
Acid amides (N, N-dimethylformamide, N, N-
Dimethylacetamide etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride etc.), dimethyl sulfoxide and vegetable oils (soybean oil, cottonseed oil etc.). Examples of the gaseous carrier include fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether and carbon dioxide gas.

Examples of the surfactant include alkyl sulfate ester salts, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and their polyoxyethylenated products, polyethylene glycol ethers, polyhydric alcohol esters and sugar alcohols. Examples include derivatives. Other auxiliaries for formulation include fixing agents, dispersants, stabilizers, and the like, specifically, casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, Synthetic water-soluble polymer (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, etc.),
PAP (isopropyl acid phosphate), BHT (2,6-
Di-tert-butyl-4-methylphenol), BH
A (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, fatty acid and fatty acid ester.

Examples of base materials for poison baits include bait ingredients such as cereal flour, vegetable oil, sugar and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, and pepper powder. Examples include food intake preventives for children and pets, cheese flavors, onion flavors, and pest-attracting flavors such as peanut oil.

Further, the pest control method of the present invention is usually carried out by applying the pesticide of the present invention to a pest or a habitat of the pest.

When the insecticide of the present invention is used for controlling agricultural and forestry pests, the application amount is usually 0.1 to 1000 g per 1000 m ² of the present compound. Emulsions, wettable powders, flowable agents, microcapsules, etc. are usually diluted with water so that the concentration of active ingredient is 10 to 10,000 ppm, and granules, powders, etc. are applied as they are. The insecticide of the present invention may be directly sprayed on plants such as crops to be protected from pests, or may be treated to the origin of the crops to be protected from pests, or by treating these preparations with soil. It can also control pests that inhabit the soil.

When the insecticide of the present invention is used for epidemic prevention, emulsions, wettable powders, flowable agents, etc. are usually diluted with water so that the concentration of the active ingredient is 0.01 to 10000 ppm, and applied. Apply directly to aerosols, smoke agents, poison baits, etc.

Further, the insecticide of the present invention is used together with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feeds and the like. It can also be used. Examples of such insecticides, acaricides and nematicides include fenitrothion, fenthion, pyridafenthion, diazinon, chlorpyrifos, chlorpyrifosmethyl, acephate, methidathione, disulfoton, DDVP, sulprophos, profenophos, cyanophos, dioxabenzophos, Organophosphorus compounds such as dimethoate, fentoate, malathion, trichlorfon, azinphos-methyl, monocrotophos, dicrotophos, ethione, fosthiate, BPMC, benfuracarb, propoxur, carbosulfan, carbaryl,
Carbamate compounds such as Mesomil, Ethiophenecarb, Aldicarb, Oxamyl, Phenothiocarb, Thiodicarb,

Etofenprox, fenvalerate, esfenvalerate, fenpropatorin, cypermethrin, α-cypermethrin, Ζ-cypermethrin, permethrin, cyhalothrin, λ-cyhalothrin,
Pyrethroid compounds such as cyfluthrin, β-cyfluthrin, deltamethrin, cycloprothrin, τ-fluvalinate, flucitrinate, bifenthrin, acrinathrin, tralomethrin, silafluofen, and halfenprox.

Neonicotinoid compounds such as acetamiprid, thiamethoxam and thiacloprid, benzoylphenylurea compounds such as chlorfluazuron, teflubenzuron, flufenoxuron and rufenuron, benzoylhydrazide compounds such as tebufenozide, halofenozide, methoxyphenozide, chromafenozide and the like, Thiadiazine derivatives, carteips, thiocyclam, bensultap and other nereistoxin derivatives, endosulfan, γ-BHC, chlorinated hydrocarbon compounds such as 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol, amitraz, chlordimeform Formamidine derivatives, etc., thiourea derivatives such as diafenthiuron, phenylpyrazole compounds, chlorfenapyr, pimeto Gin, spinosad, indoxacarb, bromopropylate, tetradiphone, quinomethionate, propargate, fenbutatin oxide, hexithiazox, etoxazole, clofentedine, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, fenazaquine, acequinocyl, bifenazeto, fluacrypifen, spiroclofen, spiroclofen, spiroclofen. , Milbemectin, avermectin, emamectin benzoate, azadirachtin [AZAD], polynactin complex [tetranactin, dinactin,
Trinactin] and the like.

[0037]

The present invention will be described in more detail below with reference to production examples, formulation examples, test examples, etc., but the present invention is not limited to these examples. In the Production Examples and Reference Production Examples, ¹ H-NMR data are measured with tetramethylsilane as an internal standard in a deuterated chloroform solvent unless the solvent is indicated in parentheses. In addition, in the production examples, the compound numbers represent the numbers shown in the above (Table 1) to (Table 3).

Production Example 1 288 mg of 2-chloro-6-phenyl-1,3,5-triazine and 116 mg of 2-butyn-1-ol were dissolved in 5 ml of anhydrous tetrahydrofuran, and 72 mg of sodium hydride (60% oily) was added. The mixture was stirred under ice-cooling for 5 minutes and further at room temperature for 2.5 hours. Then, ice water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried and concentrated. The obtained residue was subjected to silica gel thin layer chromatography (hexane: ethyl acetate = 4:
1)), 2- (2-butynyloxy) -6-
288 mg of phenyl-1,3,5-triazine (compound (1)) was obtained. ¹ H-NMR: 1.87 (t, 3
H), 5.12 (q, 2H), 7.45-7.65.
(M, 3H), 8.51 (dd, 2H), 8.96
(S, 1H)

Production Example 2 192 mg of 2-chloro-6-phenyl-1,3,5-triazine and 93 mg of 2-pentyn-1-ol were dissolved in 5 ml of anhydrous tetrahydrofuran, and 48 mg of sodium hydride (60% oily) was added. Stir at room temperature. After 10 minutes, 2 ml of anhydrous N, N-dimethylformamide was added,
The mixture was further stirred at room temperature for 2 hours. Then, ice water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. 2 organic layers with saline
It was washed twice, dried, and concentrated. The obtained residue was subjected to silica gel thin layer chromatography (developed with hexane: ethyl acetate = 4: 1) to give 2- (2-pentynyloxy) -6-phenyl-1,3,5-triazine (compound ( 2)) was obtained in an amount of 153 mg. ¹ H-NMR: 1.14
(T, 3H), 2.15-2.3 (m, 2H), 5.1
4 (t, 2H), 7.45-7.65 (m, 3H),
8.51 (dd, 2H), 8.96 (s, 1H)

Production Example 3 192 mg of 2-chloro-6-phenyl-1,3,5-triazine and 62 mg of 2-propyn-1-ol were dissolved in 5 ml of anhydrous tetrahydrofuran, and 48 mg of sodium hydride (60% oily) was dissolved therein. Was added and the mixture was stirred at room temperature for 2 hours. Then, ice water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried and concentrated. The obtained residue was subjected to silica gel thin layer chromatography (developed with hexane: ethyl acetate = 4: 1),
2- (2-propynyloxy) -6-phenyl-1,
130 mg of 3,5-triazine (compound (3)) was obtained. ¹ H-NMR: 2.54 (t, 1H), 5.15
(D, 2H), 7.45-7.65 (m, 3H), 8.
52 (dd, 2H), 8.97 (s, 1H)

Production Example 4 192 mg of 2-chloro-6-phenyl-1,3,5-triazine and 93 mg of 3-pentyn-2-ol were dissolved in 5 ml of anhydrous tetrahydrofuran, and 48 mg of sodium hydride (60% oily) was added. Stir at room temperature. After 10 minutes, 2 ml of anhydrous N, N-dimethylformamide was added,
It was stirred at room temperature for another 2 hours. Then, ice water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. 2 organic layers with saline
The extract was washed twice, dried, and concentrated. The obtained residue was subjected to silica gel thin layer chromatography (hexane: ethyl acetate =
The mixture was developed with 4: 1) to obtain 147 mg of 2- (1-methyl-2-butynyloxy) -6-phenyl-1,3,5-triazine (compound (70)). ¹ H-NMR: 1.69 (d, 3H), 1.83 (d,
3H), 5.8-5.9 (m, 1H), 7.45-7.
6 (m, 3H), 8.51 (dd, 2H), 8.95
(S, 1H)

Production Example 5 O- (2-butynyl) -S- in 30 ml of absolute ethanol.
0.8 g of methyl N- (3-fluorobenzoyl) iminomonothiol carbonate, 0.36 g of formamidine hydrochloride and 1.8 ml of triethylamine were added,
The mixture was heated under reflux for 3 hours. Then, the reaction mixture was allowed to cool to room temperature, the solvent was evaporated under reduced pressure, ice water was added to the obtained residue, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine,
After drying, it was concentrated. The residue was subjected to silica gel thin layer chromatography (developed with hexane: ethyl acetate = 5: 1) to give 2- (2-butynyloxy) -6- (3-fluorophenyl) -1,3,5-triazine (compound ( 6)) was obtained. ¹ H-NMR: 1.87 (t, 3 H), 5.11 (q,
2H), 7.2-7.3 (m, 1H), 7.4-7.5.
(M, 1H), 8.15-8.25 (m, 1H), 8.
25-8.35 (m, 1H), 8.97 (s, 1H)

Production Example 6 O- (2-butynyl) -S- in 30 ml of absolute ethanol.
0.8 g of methyl N- (2-fluorobenzoyl) iminomonothiol carbonate, 0.36 g of formamidine hydrochloride and 1.8 ml of triethylamine were added,
The mixture was heated under reflux for 3 hours. Then, the reaction mixture was allowed to cool to room temperature, the solvent was concentrated under reduced pressure, ice water was added to the obtained residue, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried, and concentrated. The residue was subjected to silica gel thin layer chromatography (developed with hexane: ethyl acetate = 5: 1) to give 2- (2-butynyloxy) -6- (2-fluorophenyl) -1,3,5-triazine (compound ( 5))
Was obtained. ¹ H-NMR: 1.87 (t, 3
H), 5.10 (q, 2H), 7.15-7.35.
(M, 2H), 7.45-7.6 (m, 1H), 8.2
-8.3 (m, 1H), 9.02 (s, 1H)

Production Example 7 O- (2-butynyl) -S- in 30 ml of absolute ethanol.
Methyl N- (2,3-difluorobenzoyl) iminomonothiol carbonate 0.85 g, formamidine hydrochloride 0.36 g and triethylamine 1.8 ml were added, and the mixture was heated under reflux for 3 hours. Then, the reaction mixture was allowed to cool to room temperature, the solvent was distilled off under reduced pressure, 5 ml of ethanol and ice water were added to the obtained residue, and the generated precipitate was collected. This was subjected to silica gel thin layer chromatography (developed with hexane: ethyl acetate = 7: 1) to give 2- (2-butynyloxy) -6- (2,3-difluorophenyl).
Add -1,3,5-triazine (compound (16)) to 0.1
6 g were obtained. ¹ H-NMR: 1.87 (t, 3H), 5.
11 (q, 2H), 7.15-7.3 (m, 1H),
7.3-7.45 (m, 1H), 7.95-8.05
(M, 1H), 9.03 (s, 1H)

Production Example 8 O- (2-butynyl) -S- in 20 ml of absolute ethanol
Methyl N- (phenylacetyl) iminomonothiol carbonate 0.42 g, formamidine hydrochloride 0.2
4 g and 1.2 ml of triethylamine were added, and the mixture was heated under reflux for 3 hours. Then the reaction mixture was allowed to cool to room temperature,
The solvent was evaporated under reduced pressure, ice water was added to the obtained residue, and the mixture was extracted with ethyl acetate. The organic layer was dried and then concentrated.
The residue was subjected to silica gel thin layer chromatography (hexane:
Ethyl acetate = 3: 1), 2-benzyl-6
0.09 g of-(2-butynyloxy) -1,3,5-triazine (the present compound (40)) was obtained. ¹ H-N
MR: 1.84 (t, 3H), 4.13 (s, 2H),
5.00 (q, 2H), 7.2-7.45 (m, 5
H), 8.81 (s, 1H)

Production Example 9 184 mg of 2-butynyloxy-6-chloro-1,3,5-triazine, 166 mg of potassium carbonate and 108 mg of orthocresol were added to 2 ml of anhydrous dimethyl sulfoxide.
Was added and stirred on an oil bath at 60 ° C. for 2 hours. The reaction mixture was allowed to cool to room temperature, brine was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried and concentrated, and the obtained residue was subjected to silica gel thin layer chromatography (developed with hexane: ethyl acetate = 5: 1) to give 2- (2-butynyloxy) -6. 115 mg of-(2-methylphenoxy) -1,3,5-triazine (the present compound (63)) was obtained. ¹ H-NMR: 1.86 (t, 3 H), 2.19 (s,
3H), 4.95 (q, 2H), 7.05-7.3.
(M, 4H), 8.66 (s, 1H)

Production Example 10 184 mg of 2-butynyloxy-6-chloro-1,3,5-triazine, 166 mg of potassium carbonate and 121 m of N-ethylaniline were added to 2 ml of anhydrous dimethyl sulfoxide.
g was added, and the mixture was stirred on an oil bath at 60 ° C. for 2 hours. The reaction mixture was allowed to cool to room temperature, brine was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried and concentrated, and the obtained residue was subjected to silica gel thin layer chromatography (developed with hexane: ethyl acetate = 3: 1) to give 2- (2-butynyloxy) -6. -(N-ethylanilino) -1,3,5-triazine (compound (67))
159 mg was obtained. ¹ H-NMR: 1.25 (t, 3H), 1.85 (br
s, 3H), 4.01 (q, 2H), 4.5-5.1.
(Br, 2H), 7.2-7.5 (m, 5H), 8.2
-8.5 (br, 1H)

Next, a method for producing an intermediate for producing this compound will be described as a reference production example. Reference Production Example 1 Most of 4.70 g of benzamidine hydrochloride was dissolved in 17 ml of water, 1.92 g of sodium hydrogencyanamide was added, and the mixture was stirred at room temperature for 7 hours under a nitrogen atmosphere. The white solid thus produced was collected, washed with water and dried to obtain 3.27 g of N-cyanobenzamidine. ¹ H-NMR (CDCl ₃ + DMSO-d ₆ 2 drops): 7.25 (b
r, 1H), 7.46 (t, 2H), 7.57 (t, 1)
H), 7.91 (d, 2H), 8.4 (br, 1H) 2.65 g of phosphorus oxychloride was added dropwise to 1.26 g of anhydrous N, N-dimethylformamide on a water bath and stirred at room temperature for 10 minutes. Then, add 10 ml of anhydrous acetonitrile,
Stir for another 30 minutes. In the water bath, 2.09 g of N-cyanobenzamidine was added to the solution in 50 m of anhydrous acetonitrile.
The solution dissolved in 1 was added dropwise, and the mixture was stirred at room temperature for 1 hour. Ice water was added, and the resulting white solid was collected by filtration, washed with water and dried to give 2
-Chloro-6-phenyl-1,3,5-triazine 1.
11 g were obtained. ¹ H-NMR: 7.5-7.7 (m, 3H), 8.52
(Dd, 2H), 9.04 (s, 1H)

Reference Production Example 2 20 ml of anhydrous toluene was charged with 10.6 of potassium thiocyanate.
9 g and 3-fluorobenzoyl chloride 15.85
g was added and the mixture was heated under reflux for 4 hours. Then the reaction mixture was cooled to room temperature and then filtered. Then 200 ml of carbon tetrachloride and 7.0 g of 2-butyn-1-ol were added to the filtrate.
Was added and the mixture was heated to reflux for 1 hour. The reaction mixture was cooled to room temperature and then concentrated. 40 ml of diethyl ether to the residue
And 60 ml of hexane were added, and the mixture was cooled on a dry ice-acetone bath to obtain a pale yellow-green solid, which was collected by filtration to give O- (2-butynyl) N- (3-fluorobenzoyl) thiocarbamate 15 0.09 g was obtained. ¹ H-NMR: 1.90 (t, 3 H), 5.16 (q,
2H), 7.25-7.35 (m, 1H), 7.45-
7.65 (m, 3H), 9.1 (brs, 1H) O- (2-butynyl) N- (3-
11.30 g of (Fluorobenzoyl) thiocarbamate and 6.6 g of methyl iodide were added, 8.97 g of a 28% methanol solution of sodium methoxide was added dropwise on a water bath, and the mixture was left at room temperature overnight. Then, a pale blue-green solid produced by adding ice to the reaction mixture was collected by filtration. The solid was washed twice with water and once with a small amount of cold methanol and then dried to obtain O- (2-butynyl) -S-methyl N.
3.10 g of-(3-fluorobenzoyl) iminomonothiol carbonate was obtained. ¹ H-NMR: 1.92 (t, 3 H), 2.45 (s,
3H), 5.06 (q, 2H), 7.2-7.3 (m,
1H), 7.35-7.45 (m, 1H), 7.85-
7.95 (m, 1H), 7.95-8.0 (m, 1H)

Reference Production Example 3 20 ml of anhydrous toluene was charged with 10.6 of potassium thiocyanate.
9 g and 2-fluorobenzoyl chloride 15.85
g was added and the mixture was heated under reflux for 4 hours. Then the reaction mixture was cooled to room temperature and then filtered. Then, 200 ml of carbon tetrachloride and 7.0 g of 2-butyn-1-ol were added to the filtrate.
g was added and the mixture was heated to reflux for 1 hour. The reaction mixture was cooled to room temperature and then concentrated. 40m of diethyl ether on the residue
1 and 40 ml of hexane were added thereto, and the mixture was cooled on a dry ice-acetone bath to collect a white solid, which was collected by filtration to obtain 15.02 g of O- (2-butynyl) N- (2-fluorobenzoyl) thiocarbamate. Obtained. ¹ H-NMR: 1.89 (t, 3 H), 5.15 (q,
2H), 7.15-7.35 (m, 2H), 7.55-
7.65 (m, 1H), 8.05-8.15 (m, 1
H), 9.7 (br d, 1H) O- (2-butynyl) N- in 45 ml of anhydrous methanol.
(2-Fluorobenzoyl) thiocarbamate 11.3
0 g and 6.6 g of methyl iodide were added, 8.97 g of 28% methanol solution of sodium methoxide was added dropwise on a water bath, and the mixture was left at room temperature overnight. Thereafter, ice was added to the reaction mixture, and the precipitated pale yellow solid was collected by filtration. The solid was washed twice with water and once with a small amount of cold methanol, and then dried to obtain O- (2-butynyl) -S-methyl N- (2-.
5.98 g of fluorobenzoyl) iminomonothiol carbonate was obtained. ¹ H-NMR: 1.90 (t, 3
H), 2.45 (s, 3H), 5.02 (q, 2H),
7.05-7.2 (m, 2H), 7.4-7.5 (m,
1H), 8.05-8.1 (m, 1H)

Reference Production Example 4 Potassium thiocyanate 10.6 was added to 20 ml of anhydrous toluene.
9 g and 2,3-difluorobenzoyl chloride 1
7.66 g was added and the mixture was heated under reflux for 4 hours. Then, the reaction mixture was cooled to room temperature and then filtered. 100 ml of carbon tetrachloride and 7.0 g of 2-butyn-1-ol were added to the filtrate.
Was added and the mixture was heated to reflux for 1 hour. The reaction mixture was cooled to room temperature and then concentrated, and 40 ml of diethyl ether and 40 ml of hexane were added to the residue and the mixture was cooled on a dry ice-acetone bath. The resulting cream-colored solid was collected by filtration to obtain 14.71 g of O- (2-butynyl) N- (2,3-difluorobenzoyl) thiocarbamate. ¹ H-NMR: 1.89 (t, 3 H), 5.14 (q,
2H), 7.2-7.3 (m, 1H), 7.35-7.
5 (m, 1H), 7.7-7.8 (m, 1H), 9.5
(Br d, 1H) O- (2-butynyl) N- in 30 ml of anhydrous methanol
(2,3-difluorobenzoyl) thiocarbamate 1
1.30 g and methyl iodide 4.40 g were added, and a 28% methanol solution of sodium methoxide 5.9 was added on a water bath.
8 g was added dropwise and left overnight at room temperature. Then, a cream-colored solid formed by adding ice to the reaction mixture was collected by filtration, washed with water twice and once with a small amount of cold methanol, and then dried to obtain O- (2-butynyl)-. 6.09 g of S-methyl N- (2,3-difluorobenzoyl) iminomonothiol carbonate was obtained. ¹ H-NMR: 1.90 (t, 3 H), 2.46 (s,
3H), 5.03 (q, 2H), 7.05-7.15.
(M, 1H), 7.25-7.4 (m, 1H), 7.7
5-7.85 (m, 1H)

Reference Production Example 5 2-butyn-1-ol 7.0 in 160 ml of carbon tetrachloride
g and 16.32 g of benzoyl isothiocyanate were added and the mixture was heated under reflux for 1 hour. Then, the reaction mixture was cooled to room temperature and then concentrated. Diethyl ether 4 in the residue
Add 0 ml and 20 ml of hexane and add dry ice-
Cooled on an acetone bath. The resulting cream-colored solid was collected to give 14.81 g of O- (2-butynyl) N-benzoylthiocarbamate. ¹ H-NMR: 1.89 (t, 3 H), 5.17 (q,
2H), 7.45-7.65 (m, 3H), 7.83.
(Dd, 2H), 9.15 (brs, 1H) O- (2-butynyl) N- in 30 ml of anhydrous methanol.
6.99 g of benzoyl thiocarbamate and 4.4 g of methyl iodide were added, to which 28 g of sodium methoxide was added.
% Methanol solution (5.98 g) was added dropwise and the mixture was left at room temperature overnight. Thereafter, a cream-colored solid filter formed by adding ice water to the reaction mixture was collected, washed successively with water twice and a small amount of cold methanol once, and then dried to obtain O- (2
-Butynyl) -S-methyl N-benzoyliminomonothiol carbonate 6.05 g was obtained. ¹ H-NMR: 1.91 (t, 3H), 2.44 (s,
3H), 5.06 (q, 2H), 7.4-7.6 (m,
3H), 8.17 (dd, 2H)

Reference Production Example 6 Potassium thiocyanate 10.6 was added to 20 ml of anhydrous toluene.
9 g and 15.46 g of phenylacetyl chloride were added, and the mixture was heated under reflux for 4 hours. Then, the reaction mixture was cooled to room temperature and then filtered. Then, carbon tetrachloride 1 in the filtrate
00 ml and 2-butyn-1-ol 7.0 g were added, and the mixture was heated under reflux for 1 hr. The reaction mixture was cooled to room temperature and then concentrated. 40 ml of diethyl ether and 40 ml of hexane were added to the residue, and the mixture was cooled on a dry ice-acetone bath. Collect the light-skinned solids that formed and collect O-
(2-Butynyl) N- (phenylacetyl) thiocarbamate (8.66 g) was obtained. ¹ H-NMR: 1.87 (t, 3 H), 3.89 (s,
2H), 5.07 (q, 2H), 7.2-7.45
(M, 5H), 8.55 (br s, 1H) O- (2-butynyl) N- in 30 ml of anhydrous methanol.
4.94 g of (phenylacetyl) thiocarbamate and 2.84 g of methyl iodide were added, and 3.86 g of a 28% methanol solution of sodium methoxide was added dropwise under ice cooling, and the mixture was allowed to stand at room temperature overnight. Then, ice water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. Dry the organic layer,
Concentrated. The residue was subjected to silica gel column chromatography (eluted with hexane: ethyl acetate = 7: 1), and O-
0.53 g of (2-butynyl) -S-methyl N- (phenylacetyl) iminomonothiol carbonate was obtained. ¹ H-NMR: 1.87 (t, 3H), 2.36 (s, 3)
H), 3.76 (s, 2H), 4.81 (q, 2H),
7.2-7.4 (m, 5H)

Reference Production Example 7 A solution prepared by dissolving 52.95 g of sodium dicyanamide in 200 ml of water was added to 265 ml of concentrated hydrochloric acid at -18 ° C.
The mixture was stirred at the same temperature for 15 minutes. Then, the mixture was stirred at 30 ° C. for 5 minutes and then cooled with ice. The resulting solid was collected by filtration, washed with a small amount of cold water and dried to give N-cyanochloroformamidine 33.
8 g was obtained. ¹ H-NMR (DMSO-d6): 6.8 (brs, 2H) Anhydrous N, N-dimethylformamide (29.04 g) was dissolved in anhydrous methylene chloride (500 ml), and phosphorus oxychloride (50.61 g) was added dropwise thereto. The mixture was stirred at 25 ° C for 5 minutes.
33.8 g of N-cyano chloroformamidine was added here, and it stirred at room temperature overnight. Then, ice water was added to the reaction mixture, and the mixture was separated from methylene chloride. The organic layer was washed twice with water and once with brine, dried and concentrated to give 2,4
18.74 g of dichloro-1,3,5-triazine was obtained as a white solid. ¹ H-NMR: 8.92 (s, 1 H) 2,4-dichloro-in 50 ml of anhydrous tetrahydrofuran
To a solution containing 1.75 g of 1,3,5-triazine and 1.75 g of 2-butyn-1-ol, 1.04 g of sodium hydride (60% oily) was added little by little under ice cooling. The mixture was cooled under ice for 4.5 hours. Then, ice water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried, and concentrated. Acetonitrile and hexane were added to the residue for liquid separation, and the acetonitrile layer was concentrated. The residue was subjected to silica gel column chromatography (hexane:
Elution with ethyl acetate = 10: 1) gave 2.99 g of 2- (2-butynyloxy) -6-chloro-1,3,5-triazine. ¹ H-NMR: 1.87 (t, 3H), 5.06 (q,
2H), 8.76 (s, 1H)

Next, formulation examples are shown. In addition, a part represents a weight part. This compound is represented by the compound numbers shown in (Table 1) to (Table 3). Formulation Example 1 9 parts of the present compounds (1) to (73) are dissolved in 37.5 parts of xylene and 37.5 parts of dimethylformamide, and 10 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are dissolved therein. , And well mixed with stirring to obtain an emulsion. Formulation Example 2 9 parts of the present compounds (1) to (73) were added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and 65 parts of silica earth, and mixed well. Stir-mix to obtain wettable powder.

Formulation Example 3 3 parts of the present compounds (1) to (73), 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate,
Bentonite (30 parts) and clay (57 parts) were added, mixed well by stirring, and then an appropriate amount of water was added to these mixtures,
Further, the mixture is stirred, granulated by a granulator, and dried by ventilation to obtain granules. Formulation Example 4 4.5 parts of the present compounds (1) to (73), 1 part of synthetic hydrous silicon oxide fine powder, and drires B (manufactured by Sankyosha) 1 as an aggregating agent
Parts and 7 parts of clay are mixed well in a mortar and then mixed by stirring with a juice mixer. Cut clay 8 into the obtained mixture.
6.5 parts was added and mixed thoroughly with stirring to obtain a dust.

Formulation Example 5 10 parts of the present compounds (1) to (73), 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt and 55 parts of water are mixed and finely ground by a wet grinding method. To obtain a formulation.

Next, the effectiveness of the insecticide of the present invention will be shown by test examples. Test Example 1 The test compound formulation obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm, to prepare a test spray solution. On the other hand, cucumber was planted in a polyethylene cup and allowed to grow until the first true leaf developed, and about 20 cotton aphids were parasitized there. One day later, the test spray solution was sprayed onto the cucumber at a rate of 20 ml / cup. Six days after spraying, the number of cotton aphids was examined, and the control value was calculated by the following formula. Control value (%) = {1- (Cb × Tai) / (Cai × T
b)} × 100 The letters in the formula have the following meanings. Cb: Number of insects before treatment in untreated plot Cai: Number of insects in untreated plot observed Tb: Number of insects in treated plot before treatment Tai: Number of insects observed in treated plot As a result, the compound (1) , (2), (3), (5),
The agents containing (6), (16), (40) and (63) as active ingredients each showed a control value of 90% or more.

Test Example 2 The test compound formulation obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm, to prepare a test spray solution. On the other hand, a cucumber was planted in a polyethylene cup and allowed to grow until the first true leaf developed, and the cucumber was sprayed with the test spray solution at a rate of 20 ml / cup. After the drug solution sprayed on the cucumber has dried, the first true leaf is cut off and a polyethylene cup (diameter 110 m
Place it on a filter paper (diameter 70 mm) containing water in m),
Thirty larvae of Thrips palmatum were released there, and the polyethylene cup was covered. Seven days later, the degree of damage to the leaves of the cucumber caused by Thrips palmatum was investigated. As a result, the area ratio of the damaged areas of Thrips palmi Rhizoma in the leaves treated with the drug containing the compounds (1), (3), (5) and (6) as the active ingredient was within 10%.

Test Example 3 The preparation of the test compound obtained in Preparation Example 5 was diluted so that the active ingredient concentration was 500 ppm, to prepare a test spray solution. On the other hand, cabbage was planted in a polyethylene cup, allowed to grow until the first true leaf developed, and then the leaves other than the first true leaf were excised. About 200 adult whitefly whiteflies were released here for about 24 hours to lay eggs on the cabbage first true leaf. The cabbage on which about 80 to 100 silver leaf whitefly eggs thus obtained were laid in a greenhouse for 3 days, and then the test spray solution was sprayed at a rate of 20 ml / cup. The number of surviving insects was examined 7 days after the application. As a result, the present compound (1),
(2), (3), (5), (6), (63) and (7
The number of surviving larvae in cabbage leaves treated with a drug containing 0) as an active ingredient was 10 or less each.

Test Example 4 The preparation of the test compound obtained in Preparation Example 5 was diluted so that the active ingredient concentration was 500 ppm, to prepare a test spray solution. On the other hand, the soil clay Bonsol 2 in a polyethylene cup
No. 50 (Sumitomo Chemical Co., Ltd.) was added and 10 seeds were added.
After seeding -15 seeds and growing them until the second true leaf was developed, the test spray solution was sprayed at a rate of 20 ml / cup onto rice that had been cut to a height of 5 cm. After the chemical solution spray-treated on rice was dried, 30 first-instar larvae of the brown planthopper were released and allowed to stand in a greenhouse <25 ° C>. Six days after the release of the larvae of the brown planthopper, the number of the planthopper parasitic on the rice was examined. As a result, the compounds of the present invention (1), (2), (3), (5), (6), (1
6), (63), (67) and (70) were treated with the drug as an active ingredient, and the number of the brown planthoppers parasitic on the cups 6 days after the treatment was 3 or less, respectively.

Test Example 5 The preparation of the test compound obtained in Preparation Example 5 was diluted so that the active ingredient concentration was 55.5 ppm, to prepare a test drug solution. On the other hand, 50 g of Baisho Bonsol No. 2 (Sumitomo Chemical Co., Ltd.) was placed in a polyethylene cup having 5 holes with a diameter of 5 mm at the bottom, and 10 to 15 seeds were sown.
The rice grown until the second true leaf developed was treated by absorbing 45 ml of the test drug solution prepared as described above from the bottom of the cup. Then, in the greenhouse <25
After standing for 6 days at 5 ° C.>, the rice was cut to a height of 5 cm, 30 first-instar larvae of the brown planthopper were released, and they were left at <25 ° C.> in a greenhouse. Six days after the release of the larvae of the brown planthopper, the number of the planthopper parasitic on the rice was examined. As a result, the compounds of the present invention (1), (2),
In the cup treated with the drug containing (5) and (6) as the active ingredient, the number of parasites 6 days after the release was 3 or less, respectively.

[0063]

The insecticide of the present invention has excellent insecticidal activity against various pests.

Claims (4)

[Claims] 1. A formula (1) [Wherein R ¹ is C optionally substituted by a halogen atom]
Represents a 3-C7 alkynyl group, R ² is a halogen atom, C
1-C4 alkyl group, C1-C3 haloalkyl group, C1
It represents a -C4 alkoxy group, a C1-C4 haloalkoxy group, a cyano group or a nitro group, and n represents an integer of 0-5.
However, when n represents an integer of 2 or more, R ² may be the same or different. A represents a single bond, a CR ³ R ⁴ group, an oxygen atom, a sulfur atom or an NR ⁵ group. R ³ and R ⁴ each independently represent a hydrogen atom or a C1-C4 alkyl group, and R ⁵ represents a C1-C4 alkyl group or a hydrogen atom. ] The 1,3,5-triazine compound shown by these is contained as an active ingredient, The insecticide characterized by the above-mentioned. 2. The insecticide according to claim 1, wherein R ¹ is a 2-butynyl group or a 2-pentynyl group. 3. A pest control method comprising applying an effective amount of a 1,3,5-triazine compound represented by the formula (1) to a pest or a habitat of the pest. 4. 2- (2-Butynyloxy) -6-phenyl-1,3,5-triazine