JPH06220021A - Pyridazinone derivative and insecticidal, acaricidal agent - Google Patents

Abstract

PURPOSE:To provide a novel pyridazinone derivative having strong insecticidal, acaricidal activities against various agricultural insect pests, exhibiting excellent control effects against various resistant insect pests causing agricultural problems, and low in toxicity. CONSTITUTION:A pyridazinone derivative of formula 1 [R is H, alkyl, alkoxyalkyl, (substituted)phenyl], e.g. 2-t-butyl-4-chloro-5-[4(2-n-butyl) ethenyl]benzylthio-3(2H)-pyridazinone. The compound of formula 1 is obtained e.g. by reacting a pyridazinone derivative of formula 2 with a benzylhalide compound of formula 3 (X is halogen) in the presence of an acid-binding agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pyridazinone derivative and an insecticidal and acaricidal agent containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art It is known that certain compounds among pyridazinone derivatives are effective as insecticides and acaricides. For example, JP-A 61-17570 discloses 2-t-butyl-4-chloro-5- (4-n-hexyl) benzylthio-3 (2H) -pyridazinone. In addition, in JP-A-62-27736, 2
-T-butyl-4-chloro-5- (4-vinyl) benzylthio-3 (2H) -pyridazinone and the like are described. However, these compounds cannot be said to have a sufficient drug effect.

[0003]

[Means for Solving the Problem] The present inventors have conducted various studies on pyridazinone derivatives in order to develop a drug having a strong insecticidal and acaricidal activity against various agricultural pests based on the above-mentioned circumstances, General formula (1)

[0004]

[Chemical 2]

[In the formula, R represents a hydrogen atom, an alkyl group, an alkoxyalkyl group or a phenyl group which may have 1 or 2 substituents at any position. The pyridazinone derivative represented by the above is a novel compound not described in the literature, and has extremely strong insecticidal and acaricidal activity,
In addition, the present invention was completed by confirming that it exerts an excellent controlling effect against various resistant pests which are agricultural problems and has low toxicity.

The compounds of the present invention represented by the above general formula (1) are useful as insecticides and acaricides. The pests on which the compound of the present invention acts particularly effectively include, for example, Chacococca esculenta, Plutella xylostella, Caterpillars, Tamanaginuwawaba,
Lepidopteran pests such as White-spotted armyworm, Spodoptera litura,
Colorado potato beetle
etle), Mexican bean beetle (Mexica)
n Bean Beetle) and other beetle insects, green peach aphid, cotton aphid, bean aphid, leafhopper leafhopper, leafhopper leafhopper, leafhopper leafhopper, leafhopper plant, white-necked planthopper, white-leafed beetle, white-flying whitefly, pests of whitefly, whitefly, whitefly Examples thereof include pests of the order Thysanoptera such as thrips, pests of the mites family such as Nami mites, kanzawa mites, citrus mites, pests of the fungus mite family such as citrus rust mite, and pests of the dust mite family such as Chanod mite mite.

The compounds of the present invention are superior to conventional pyridazinone derivatives in that they are effective against a wide range of harmful insects. In particular, the compound of the present invention exhibits excellent insecticidal activity against drug-resistant pests, which were not sufficiently effective with conventional pyridazinone derivatives. The compound of the present invention has a fast-acting insecticidal activity, especially against the insect pests of the order Lepidoptera such as diamondback moth and Spodoptera litura.

Further, the compound of the present invention has antifeedant activity and growth inhibitory activity against the above-mentioned harmful insects.

Further, the compound of the present invention has not only an insecticidal activity against the above-mentioned adult pests, but also an effect of suppressing the hatching of eggs.

Among the compounds of the present invention, a pyridazinone derivative represented by the general formula (1), wherein R is a C _{1 to} C ₅ straight chain or branched chain alkyl group, particularly a straight chain or branched chain group wherein R is C ₄ The pyridazinone derivative of the general formula (1), which is an alkyl group, is a preferable compound because it can exhibit various properties such as excellent insecticidal activity against an extremely wide range of harmful insects.

The compound of the present invention is produced, for example, by the method shown in the following reaction formula-1.

[0012]

[Chemical 3]

[In the formula, R is the same as above. X represents a halogen atom. That is, the compound of the present invention is produced by reacting the pyridazinone derivative represented by the general formula (2) with the benzyl halides represented by the general formula (3) in the presence of an acid binder. Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, hydrocarbons such as benzene and toluene, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and 1,4-dioxane, acetonitrile, propionitrile. And amides such as N, N-dimethylformamide and hexamethylphosphoric triamide. If necessary, a mixed solvent of these solvents and water can also be used. The ratio of the pyridazinone derivative represented by the general formula (2) to the benzyl halide represented by the general formula (3) is usually about 0.5 to 2 times, preferably equimolar to the latter.
It is preferable that the molar ratio is about 1.5 times. A wide variety of known acid binders can be used. Specific examples include tertiary amines such as triethylamine and pyridine, alkali metal salts such as sodium carbonate and potassium carbonate, and alkali metal salts such as sodium hydroxide and potassium hydroxide. A hydroxide etc. can be illustrated. The amount of such an acid binder used is usually an equimolar to 2-fold molar amount, and preferably an equimolar to 1.2-fold molar amount with respect to the compound (2). The reaction proceeds well in the range from room temperature to the boiling point of the solvent used,
Generally, it is completed in about 1 to 5 hours.

The compound (2) used as a starting material in the above reaction formula-1 is a known compound, and is a known method, for example, Angew. Chem. Internat. Edit. 4 (4).
It is easily produced according to the method described in 300 (1965). The other starting material, the compound (3), has the following reaction formula-
It can be easily manufactured by the method shown in 2.

[0015]

[Chemical 4]

The compound (3) is obtained by halogenating the compound (4) by a conventional method, for example, using a thionyl halide such as thionyl chloride and thionyl bromide or a halogenating agent such as phosphorus trichloride and phosphorus tribromide. Is produced in good yield.

The compound of the present invention obtained by the above method can be easily isolated and purified from the reaction mixture by a conventional separation means such as solvent extraction, recrystallization and column chromatography. Therefore, according to the above production method, the compound of the present invention can be produced in high yield and high purity.

When the compound of the present invention is used as an insecticide or acaricide, an emulsion, a wettable powder, a suspension, a fine granule, a powder,
It may be used in various forms such as a wettable powder, a coating agent, a foam spray preparation, a microcapsule preparation, an aerosol preparation, a preparation impregnated with a natural or synthetic substance, a fumigation preparation, and a preparation for concentrated and small amount spraying. In preparing these formulations, various surfactants can be used for emulsification, dispersion, suspension and foaming. Examples of such a surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester and the like as a nonionic surfactant, and alkylbenzene sulfonate, alkyl as an anionic surfactant. Sulfosuccinate, alkyl sulphate, polyoxyethylene alkyl sulphate, allyl sulphonate,
Examples thereof include lignin sulfite. As the solubilizer, diluent and carrier, various organic solvents, various aerosol propellants, various natural minerals and plants, and various synthetic compounds can be used. Particularly preferred among the organic solvents are benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene, dichloromethane, chloroethylene, cyclohexane, cyclohexanone, acetone, methylethylketone, methylisobutylketone, alcohols, dimethylformamide, dimethylsulfoxide, Acetonitrile, naphtha, mineral oil fraction, etc. can be illustrated. Examples of aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen, carbon dioxide and the like. Examples of the mineral substances include kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, chalk, calcite, pumice, sepiolite and dolomite. Examples of plants include walnut shells, tobacco stems, sawdust, and the like. Examples of synthetic compounds include alumina, silicates, sugar polymers and the like. As an adhesive,
Examples include carboxymethyl cellulose, gum arabic, polyvinyl alcohol, and polyvinyl acetate.
It is also possible to color these preparations with an organic or inorganic dye. In the present invention, in producing the above various preparations, the compound of the present invention may be prepared to be contained in an amount of about 0.1 to 95% by weight, preferably about 0.5 to 90% by weight.

When the compound of the present invention is made into an emulsion, it has excellent solubility in a commonly used petroleum carbon-based organic solvent such as naphtha and xylene as compared with conventional pyridazinone derivatives. Higher concentration is possible, which is convenient for transportation and storage of emulsion.

The prepared preparation may be used as it is or after being diluted with a carrier or water.
It can be freely diluted within the range of 0001 to 100% by weight, and preferably, it is used by diluting it so as to contain about 0.0001 to 10% by weight of the compound of the present invention. The amount to be sprayed varies depending on the occurrence of insects and mites, weather conditions, etc. and cannot be generally stated, but in general, the compound of the present invention is about 0.1 to 10 kg, preferably 0.
It is preferable that the weight is about 1 to 1 kg.

[0021]

EXAMPLES Production examples and test examples of the compound of the present invention are shown below.

Production Example 1 2-t-butyl-5-mercapto-3 (2H) -pyridazinone (220 g, 0.01 mol) and 4- (2-n-).
Butyl) ethenylbenzyl bromide (2.92 g, 0.
011 mol) in methanol (20 ml) at room temperature while stirring with anhydrous sodium carbonate (2.1 g, 0.0
15 mol) is added in small portions. After the addition, the reaction mixture was stirred at room temperature for another 4 hours and then benzene (200 m
1) and water (200 ml) are added. Wash the oil layer with water,
Then it is dried over anhydrous magnesium sulfate. The residue obtained by removing the solvent was subjected to silica gel column chromatography separation using mobile phase benzene-ethyl acetate to give yellow oily 2-t-butyl-4-chloro-5- [4- (2-n-butyl) ethenyl]. Benzylthio-3 (2H) -pyridazinone (3.1
1 g, 80%). The physical properties of this compound are
o. 5 is shown in Table 1 below.

The compounds produced according to Production Example 1 are shown in Table 1.
~ Shown in Table 3.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

Test Example 1 Test for Leafhopper Green Leafhopper The compound to be tested is dissolved in acetone, and the leafhopper leafhopper (Nepho) is applied using a micro applicator manufactured by Burkard.
It was applied locally (drop size 0.5 μl / head) to the abdomen of an adult female of Tettix cinchticeps) (Miyagi strain or Nakagawara strain). The Miyagi system is a pest that does not have resistance to organophosphorus agents and carbamate agents, that is, is susceptible. The Nakagawara strain is a pest having resistance to organic phosphorus agents and carbamate agents. After the above-mentioned treatment, the rice was rolled into a plastic cup having a diameter of 13 cm and the root portion of which was wound with absorbent cotton, and was placed in an assay room (25 ± 1 ° C., humidity 40%). The number of live and dead insects was examined 48 hours after the treatment. The results are shown in Table 4.
Shown in. The numbers in the column of the test compound in Table 4 are the compound Nos. In Tables 1 to 3 above. It corresponds to. The same applies to the tables below.

[0028]

[Table 4]

From Table 4, the compounds of the present invention are not only resistant to the leafhopper leafhoppers that are not resistant to the organic phosphorus agents and carbamate agents, but are also the leafhopper leafhoppers that are resistant to the organic phosphorus agents and carbamate agents. It can be seen that it also has excellent insecticidal activity against.

Test Example 2 Diamondback moth test 2 parts by weight of the compound of the present invention were dissolved in 98 parts by weight of acetone,
This was diluted to a predetermined concentration with an aqueous solution containing 0.04% spreader (Nippon Pesticides Shin-Rinoh) to prepare a solution. 7c
mx 7 cm pieces of cabbage leaf were dipped in the solution prepared as above for 10 seconds. The fourth-instar larvae of Plutella xylostella along with the leaf pieces treated as described above were placed in a plastic cup having a diameter of 13 cm and allowed to stand in a thermostatic chamber at 25 ± 1 ° C. Process 2
The dead insect rate after 7 days and the emergence rate after 7 days were measured, and the results are shown in Table 5.

[0031]

[Table 5]

From Table 5, the compound of the present invention has an excellent insecticidal activity against diamondback moth larvae and has a low emergence rate, and therefore exhibits antifeedant activity and growth inhibitory activity against diamondback moth larvae. It is understood that it is expressed.

Test Example 3 Green peach aphid test 2 parts by weight of the compound of the present invention was dissolved in 98 parts by weight of acetone,
This was diluted to a predetermined concentration with an aqueous solution containing 0.04% spreader (Nippon Pesticides Shin-Rinoh) to prepare a solution. 7c
mx 7 cm pieces of cabbage leaf were dipped in the solution prepared as above for 10 seconds. A peach peach aphid wingless female (Naruto Y strain or Naruto R strain) was placed in a plastic cup having a diameter of 9 cm together with the leaf pieces treated as described above, and the cup was allowed to stand in a thermostatic chamber at 25 ± 1 ° C. Naruto Y strains are pests that do not have resistance to synthetic pyrethroid agents, organophosphorus agents and carbamate agents, that is, they have sensitivity. The Naruto R strain is a pest having resistance to synthetic pyrethroid agents, organic phosphorus agents and carbamate agents. The mortality rate 2 days after the treatment was measured, and the results are shown in Table 6.

[0034]

[Table 6]

From Table 6, it can be seen that the compounds of the present invention show resistance not only to the green peach aphid which has no resistance to organic phosphorus agents and carbamate agents but also to organic phosphorus agents and carbamate agents. It can be seen that it also has an excellent insecticidal activity against the green peach aphid.

Test Example 4 Nami-dani mite test 2 parts by weight of the compound of the present invention is dissolved in 98 parts by weight of acetone. This was diluted to a predetermined concentration with an aqueous solution containing 0.04% spreader (Nippon Pesticides Shin-Rinoh) to prepare a solution.
Potted kidney beans were inoculated with adult spider mite (Naruto strain or Akita strain), and then the solution prepared as described above was sprayed until the drops dripped. The Naruto strain is a pest that does not have resistance, that is, has sensitivity to sunmite and danitron. What is the Akita system?
It is a pest that has resistance to sunmite and danitron. The mortality of insects was measured 3 days after the treatment, and the results are shown in Table 7.

[0037]

[Table 7]

From Table 7, the compounds of the present invention were excellent not only against spore mite which is not resistant to sun mite and danitron, but also to spore mite which is resistant to sun mite and danitron. It is found to have insecticidal activity.

Test Example 5 Citrus mites test 2 parts by weight of the compound of the present invention are dissolved in 98 parts by weight of acetone. This was diluted to a predetermined concentration with an aqueous solution containing 0.04% spreader (Nippon Pesticides Shin-Rinoh) to prepare a solution.
Potted seedlings Wenzhou mandarin oranges were inoculated with adult citrus red mite (Naruto strain or Shizuoka strain), and then sprayed with the solution prepared as described above until the drops dripped. The Naruto strain is a pest that does not have resistance, that is, has sensitivity to sunmite and danitron. The Shizuoka strain is a pest having resistance to sunmite and danitron. The mortality of insects was measured 3 days after the treatment, and the results are shown in Table 8.

[0040]

[Table 8]

From Table 8, the compounds of the present invention are excellent not only against citrus red mite which is not resistant to sun mite and danitron but also against citrus red mite which is resistant to sanmite and danitron. It is found to have insecticidal activity.

Claims (4)

[Claims] 1. A general formula: [In the formula, R represents a hydrogen atom, an alkyl group, an alkoxyalkyl group, or a phenyl group which may have 1 or 2 substituents at arbitrary positions. ] The pyridazinone derivative represented by these. 2. The pyridazinone derivative according to claim _{1, wherein} R is a C _{1 to} C ₅ linear or branched alkyl group. 3. The pyridazinone derivative according to claim 1, wherein R is a C ₄ linear or branched alkyl group. 4. An insecticide and acaricide containing the pyridazinone derivative according to claim 1 as an active ingredient.