JPH0528226B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, X represents a fluorine atom or a chlorine atom, Y represents a hydrogen atom, a fluorine atom, or a chlorine atom, and Z represents a hydrogen atom, a fluorine atom, a bromine atom,
Represents a chlorine atom or a cyano group. ) and an insecticide containing the same as an active ingredient. Until now, the only known biological activities of pyridylpyridone derivatives are anti-inflammatory and analgesic effects (Special Publications Nos. 42-20294, 42-20295, 43
−3196 publications). The present inventors conducted synthetic research on new agricultural chemicals and found that a pyridylpyridone derivative represented by the general formula (2) (hereinafter referred to as the compound of the present invention (1)) has extremely high insecticidal efficacy. 2. Extremely effective against insecticide-resistant pests. They discovered that it has excellent properties such as, and completed the present invention. Specific pests for which the compound () of the present invention is particularly effective include Hemiptera such as planthoppers, Lepidoptera such as armyworms and diamondback moths, Diptera such as Culex mosquitoes and house flies, and Reciptera such as the German cockroach. can give. The method for producing the compound of the present invention () is as follows:
For example, [(1) 2,3-dichloro-5-trifluoromethylpyridine is heated with dimethylformamide and anhydrous sodium acetate (X=Cl, Y=H, Z
A compound of =Cl is generated. ). (2) General formula (In the formula, X and Y represent the same meanings as above, and X' represents a halogen atom.) A pyridine compound represented by the general formula (In the formula, Z represents the same meaning as above.) is heated in the presence of a base and a copper catalyst. ] can be given. In addition to the above method (2), the fluorine-substituted product and the cyano-substituted product can also be produced by a substitution reaction using the chloro-substituted compound of the present invention (). For example, a fluorine-substituted compound can be produced by reacting with potassium fluoride, cesium fluoride, etc. in a polar solvent (dimethylformamide, sulfolane, dimethylsulfoxide). Cyano-substituted compounds can also be easily produced by reacting with potassium cyanide, sodium cyanide, etc. in a polar solvent. Examples of the production of the compound () of the present invention will be shown below using reference examples. Reference Example 1 (Production of Compound (1)) 4.0 g of 2,3-dichloro-5-trifluoromethylpyridine and 1.9 g of anhydrous sodium acetate were added to 15 ml of dry dimethylformamide,
Stirred at ~150°C for 3 hours. The reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with brine and then dried over anhydrous magnesium sulfate. After distilling off ethyl acetate, it was subjected to silica gel column chromatography (developing solvent: n-hexane:
Ethyl acetate = 20:1), [1(2H),3-chloro-
1.2 g of 5-trifluoromethyl-3'-chloro-5'-trifluoromethyl-2'-bipyridin]-2-one (compound (1)) was obtained as white crystals. Melting point 108.5℃ PMR (internal standard tetramethylsilane, δ
value, solvent amount (chloroform) 7.77 (2H, S), 8.19 (1H) 8.77 (1H) IR 1680cm ^-1 (carbonyl) Reference example 2 (Production of compound (1)) 100mg (62%) of sodium hydride was dried Add 500 mg of 3-chloro-5-trifluoromethyl-2-pyridone to 10 ml of dimethylformamide.
was added at 20°C. After stirring for 15 minutes, 660 mg of 2,3-dichloro-5-trifluoromethylpyridine
and 20 mg of cuprous chloride were added and stirred at 140 to 150°C for 5 hours. It was poured into ice water and extracted with ethyl acetate.
After washing the ethyl acetate layer with brine and evaporating the solvent,
This was subjected to silica gel column chromatography (chromatography conditions were the same as in Reference Example 1) to obtain 350 mg of Compound (1) as white crystals. Reference Example 3 (Production of compound (2)) 3.0 g of compound (1) was heated at 150°C with 10 g of anhydrous potassium fluoride and 100 ml of anhydrous dimethyl sulfoxide.
The mixture was stirred for 10 hours. The reaction solution was poured into ice water and drawn with ethyl acetate. After washing the organic layer with water, the solvent was distilled off. The remaining oil was subjected to silica gel column chromatography (chromatography conditions were the same as in Reference Example 1),
1.5 g of white crystals were obtained. 2 using n-hexane
Recrystallization was performed several times to obtain 1.0 g of compound (2) as white crystals. Melting point 110.2℃ H ¹ NMR (δ, CDCl ₃ ) 7.7-8.0 (m, 3H) 8.7 (Broad S1H) F ¹⁹ NMR (CF ₃ CO ₂ H internal standard) +16.5, +15.0, -36.0 Mass spectrum 69 , 164, 228, 272,
325, 360, 36 1,362 Reference example 4 (Production of compound (3)) 500 mg of compound (1) was dissolved in anhydrous dimethyl sulfoxide 10
ml, add 130mg of sodium cyanide,
The mixture was stirred at 20°C for 1 hour. The reaction solution was poured into 30 ml of ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and then concentrated, and the remaining oil was subjected to silica gel column chromatography (chromatography conditions were the same as in Reference Example 1) to obtain 260 mg of compound (3) as white crystals. Melting point 144.2℃ H ¹ NMR (δ, CDCl ₃ ) 8.1 (m, 2H), 8.28 (d, 1H J=2Hz) 8.85 (d, 1H, J=2Hz) Mass spectrum 180, 332, 367, 368, 369 General Examples of the compounds of the present invention represented by formula () are shown below, but the present invention is not limited to these examples.

[Table] When the compound of the present invention () is used as an active ingredient of an insecticide, it may be used as it is without adding any other ingredients, but it is usually used in combination with a solid carrier, liquid carrier, gaseous carrier, or interface. It can be mixed with activators, other conditioning aids, baits, etc., or impregnated into base materials such as incense sticks and mats to produce emulsions, wettable powders, powders, granules, oils, aerosols, mosquito coils, and electricity. It is formulated into heating fumigants such as mosquito repellents, fogging agents such as fogging, non-heating fumigants, poison baits, etc. These preparations contain 0.01% to 95% by weight of the compound of the present invention as an active ingredient. Examples of solid carriers include fine powders or granules such as kaolin clay, attapalgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include defatted hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene, halogenated hydrocarbons such as dichloroethane, trichloroethylene, and carbon tetrachloride, and methanol. , alcohols such as ethanol, isopropanol, ethylene glycol, and cellosolve; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and isophorone;
Examples include ethers such as diethyl ether, dioxane, and tetrahydrofuran, esters such as ethyl acetate, nitrites such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, and vegetable oils such as dimethyl sulfoxide, soybean oil, and cottonseed oil. . Gaseous carriers include fluorocarbon gas, LPG (liquefied petroleum gas),
Examples include dimethyl ether. emulsification, dispersion,
Surfactants used for wet spreading, etc.
Alkyl sulfate group, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, Examples include nonionic surfactants such as sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester. Formulation aids such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, CMC (carboxymethyl cellulose), pine oil, agar, etc., and are stable. Agents include alkyl phosphates such as PAP (isopropyl acid phosphate) and TCP (tricresyl phosphate), vegetable oil,
Epoxidized oil, surfactants mentioned above, BHT, BHA
, fatty acid salts such as sodium oleate and calcium stearate, and fatty acid esters such as methyl oleate and methyl stearate. Examples of formulations are shown below. In addition, the compound of the present invention is the first
It is indicated by the compound number in the table, and parts indicate parts by weight. Formulation Example 1 0.2 part of the compound of the present invention (1), (3) or (5), 2 parts of xylene and 97.8 parts of white kerosene are mixed to obtain each oil agent. Formulation Example 2 Compounds of the present invention (1), (2), (3), (4), (5), (6) or (7)
)
10 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene were thoroughly mixed to obtain each emulsion. Formulation Example 3 20 parts of the compound of the present invention (2), (4) or (6), 10 parts of fenitrothion, 3 parts of calcium ligninsulfonate
1 part, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrated silicon oxide are thoroughly ground and mixed to obtain each wettable powder. Formulation Example 4 1 part of the compound (1) or (4) of the present invention, Carbaryl 2
1 part, 87 parts of kaolin clay, and 10 parts of talc are thoroughly ground and mixed to obtain each powder. Formulation Example 5 5 parts of the compound (2) or (5) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 62 parts of kaolin clay were thoroughly ground and mixed, and water was added and kneaded well. After combining, each granule is obtained by granulation and drying. Formulation Example 6 0.05 parts of the compound (3) or (6) of the present invention, 0.2 parts of tetramethrin, 0.05 parts of resmethrin, 7 parts of xylene, and 32.7 parts of deodorized kerosene are mixed and dissolved, and the mixture is filled into an aerosol container and a valve part is attached. Each aerosol is obtained by filling 60 parts of propellant (liquefied petroleum gas) under pressure through the valve part. Formulation Example 7 To 1 g of the compound (1) or (7) of the present invention, 5-propangylfurfuryl-dl-cis, 0.5 g of transchrysanthemate, and 0.5 g of BHT were added, dissolved in an appropriate amount of acetone, and 4.0 cm× Each heated smoking agent was obtained by uniformly adsorbing it onto a porous ceramic plate of 4.0 cm and 1.2 cm thick. These preparations can be used as they are or diluted with water. Also. Other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers,
It can also be used in combination with soil conditioners and the like. When the compound of the present invention () is used as a nematode agent, the application amount is usually 5 g to 10 are.
500g, and when applying emulsions, wettable powders, etc. diluted with water, the application concentration is 10ppm to 1000ppm.
Powders, granules, oils, aerosols, etc. are applied as they are without any dilution. Next, a test example is shown. The compounds used for comparison are indicated by compound symbols in Table 2.

[Table] Sir


Test Example 1 Paper of the same size was placed at the bottom of a polyethylene cup with a diameter of 5.5 cm, and 0.7 ml of a diluted solution of the emulsion of the present compound and the control compound obtained in Formulation Example 2 at a predetermined concentration with water was dropped onto the paper. . As bait, 30 mg of sucrose was placed on the paper. Among them, an insecticide-resistant domestic house fly female adult was found.
We released 10 animals, covered them, and checked whether they were alive or dead after 48 hours.
Mortality rate was determined (2 replicates). The results are shown in Table 3.

[Table] Test Example 2 Rice stems (12 cm in length) were immersed for 1 minute in a water dilution of the emulsions of the present compound and the control compound obtained in Formulation Example 2 at a predetermined concentration. After air-drying, the rice stems were placed in a test tube, 10 adult brown planthoppers were released, and one day later, they were examined to see if they were alive or dead, and the mortality rate was determined (two repetitions). The results are shown in Table 4.

[Table] Test Example 3 A piece of paper of the same size was placed on the bottom of a polyethylene cup with a diameter of 5.5 cm, and 0.7 ml of the emulsion of the present compound and the control compound obtained in Formulation Example 2 diluted with water at a predetermined concentration was placed on the paper. dripped into. As bait, 30 mg of sucrose was placed on the paper. Ten male German cockroaches were released into the container, the lid was placed on the container, and 48 hours later, the survival rate was determined to determine the mortality rate (2 repetitions).
The results are shown in Table 5.

【table】

Claims (1)

[Claims] 1. General formula (In the formula, X represents a fluorine atom or a chlorine atom, Y represents a hydrogen atom, a fluorine atom, or a chlorine atom, and Z represents a hydrogen atom, a fluorine atom, a bromine atom,
Represents a chlorine atom or a cyano group. However, X represents a chlorine atom, Y represents a hydrogen atom, and
Except when Z represents a chlorine atom. ) A pyridylpyridone derivative represented by 2 General formula (In the formula, X represents a fluorine atom or a chlorine atom, Y represents a hydrogen atom, a fluorine atom, or a chlorine atom, and Z represents a hydrogen atom, a fluorine atom, a bromine atom,
Represents a chlorine atom or a cyano group. However, X represents a chlorine atom, Y represents a hydrogen atom, and
Except when Z represents a chlorine atom. ) An insecticide characterized by containing a pyridylpyridone derivative as an active ingredient.