JPH08198855A - Pyridazinone derivative and vermin controlling agent - Google Patents

Abstract

PURPOSE: To provide the subject new compound having excellent insecticidal and miticidal activities against farm vermin and spider mites, almost harmless to mammals, fish and beneficial insects and useful as a vermin controlling agent. CONSTITUTION: This compound is a 3(2H)-pyridazinone derivative of formula I (R<1> is a 1-6C alkyl, a 3-6C alkenyl, phenethyl, cinnamyl, etc.; R<2> is H, a halogen, a 1-6C alkoxy, a 1-15C alkylsulfenyl, a 1-15C alkylsulfonyl, etc.; R<3> is a halogen-substituted methyl), e.g. 2-benzyl-5-bromodifluoromethoxy-3(2H)- pyridazinone. The compound of formula I can be produced e.g. by reacting a 4- or 5-hydroxy-3(2H)-pyridazinone derivative of formula II with a haloalkylating agent (e.g. dibromodifluoromethane or chlorodifluoromethane) in the presence of a base. The compound is preferably used in a form mixed with a proper carrier (e.g. clay or talc) and the amount of the active component to be applied to a field is preferably 0.005-50kg per 1ha.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel 3 (2H) -pyridazinone derivative and a pest control agent containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Many 3 (2H) -pyridazinone derivatives have been described in patents, literatures and the like. For example, JP-A-4-9374 describes compounds having various substituted alkoxy groups as the substituents at the 5-position of the 3 (2H) -pyridazinone ring.

[0003]

Due to the long-term use of insecticides, pests have acquired resistance in recent years, making it difficult to control them with conventional insecticides. In addition, some insecticides are highly toxic, and some are perturbing the ecosystem due to persistence. Therefore, the development of new insecticides with low toxicity and low residue is always expected.

[0004]

In view of such a situation, the present inventors have succeeded in controlling pests with a low dose and exhibiting excellent insecticidal activity and having almost no adverse effect on mammals, fish and beneficial insects. As a result of continuing research to develop agents, the general formula (1)

[0005]

Embedded image

[Wherein R¹Is C_1-6Alkyl group, C
_3-6Alkenyl, phenethyl, cinnamyl, pyri
A dimethyl group, a phenyl group substituted with a halogen atom,
Or C _1-4Alkyl group, C_1-4Haloalkyl group, nit
A group which may be substituted with a group or halogen atom
Represents a methyl group substituted with a nyl group,

R ² is hydrogen atom, halogen atom, C _1-6
Alkoxy group, C _1-15 alkylsulfenyl group, C _1-15
Alkylsulfinyl group, C _1-15 alkylsulfonyl group, phenylsulfenyl group optionally substituted with halogen atom, phenylsulfinyl group optionally substituted with halogen atom, optionally substituted with halogen atom A phenylsulfonyl group, a benzyloxy group, a phenoxy group or a phenethyl group optionally substituted with a halogen atom,

R ³ represents a methyl group substituted with a halogen atom. ] The 3 (2H) -pyridazinone derivative represented by these, and the pest-control agent characterized by containing 1 type, or 2 or more types of this derivative.

The compounds of the present invention are effective against various harmful pests at extremely low drug concentrations. As the pest,
For example, agricultural pests such as leafhopper leafhoppers, brown planthoppers, green peach aphids, red peach aphids, red stalks budworms, sphagnum moss, diamondback moth, and spider mites,
Mites such as citrus mites, kanzawa mites, hygiene pests such as Culex pipiens, houseflies, German cockroaches, ants, fleas, lice, etc. And domestic dust mites such as livestock pests, mites, deer mites and claw mites, and molluscs such as slugs and snails. That is, the compound of the present invention can effectively control pests of Orthoptera, Hemiptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Termites and mites and lice at low concentrations. On the other hand, the compounds of the present invention include extremely useful compounds that have little adverse effect on mammals, fish, crustaceans and beneficial insects.

The compound of the present invention can be synthesized by the following method (Scheme 1).

[0011]

Embedded image

(R ¹ , R ² and R ^{3 in} (Scheme 1) have the same meanings as described above, and L is a chlorine atom, a bromine atom, an iodine atom, an alkylsulfonate group or an arylsulfonate group. Represents a leaving group, and R ⁴ represents a halogenated methyl group.)

Method A in (Scheme 1) is the 4- or 5-hydroxy-3 (2) represented by the general formula (2).
A method for synthesizing the compound of the present invention by reacting a (H) -pyridazinone derivative with a haloalkylating agent in the presence of a base is shown. As the haloalkylating agent, dibromodifluoromethane, chlorodifluoromethane, dichlorodifluoromethane or the like can be used.

Method B is 3 (2) represented by the general formula (3).
A method for synthesizing the compound (1) of the present invention by alkylating a (H) -pyridazinone derivative will be shown. Method C is a method of reacting the compound (1 ′) of the present invention with a halogenating agent and converting it to another compound (1) of the present invention by a halogen exchange reaction.

Method D shows a method of reacting the compound (1 ″) of the present invention having a bromine atom on the pyridazinone ring with various nucleophiles to convert it to another compound (1) of the present invention.
In the synthetic method described in (Scheme 1), as the base to be used, alkali metal alkoxides such as sodium ethoxide, sodium methoxide and potassium t-butoxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, Examples thereof include alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as triethylamine and pyridine, and sodium hydride.

The reaction shown in Scheme 1 can be carried out in a solvent inert to the reaction, and the solvent is methanol,
Lower alcohols such as ethanol, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethers such as 1,2-dimethoxyethane and 1,2-diethoxyethane, methylene chloride. , Halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, amides such as dimethylformamide and dimethylacetamide, acetonitrile, dimethylsulfoxide, and mixed solvents thereof.

In some cases, a mixed solvent of these solvents and water may be used, and good results may be obtained by adding a quaternary ammonium salt such as tetra-n-butylammonium bromide as a catalyst. . The reaction temperature can be set to any temperature from −30 ° to 200 ° C. Further, the range of 0 ° C. to 150 ° C. or 0 ° C. to the boiling point of the solvent is preferable when a solvent is used. The base is 0.8 to 10 equivalents of the reaction substrate, preferably 0.8.
~ 3 equivalents are used.

The compound of the present invention can be obtained from the reaction solution by a conventional method, but if it is necessary to purify the compound of the present invention, it can be separated and purified by any purification method such as recrystallization or column chromatography. You can Among the compounds included in the present invention, the compounds having an asymmetric carbon include the optically active compounds (+) and (−).

The synthetic examples of the compound of the present invention will be specifically described below as examples, but the present invention is not limited thereto.

[0020]

【Example】

 [Synthesis Example 1] 2-benzyl-5-bromodifluorome
Synthesis of Toxy-3 (2H) -pyridazinone (Compound No.
1) After washing 1.3 g of sodium hydride with n-hexane,
Suspended in N, N-dimethylformamide (50 ml)
Then, under cooling with ice, 2-benzyl-5-hydroxy-3 (2
H) -Pyridazinone 5.0 g was gradually added, and the
Add 10 g of romodifluoromethane and stir at room temperature for 3 hours
did. Add 10 g of dibromodifluoromethane to this
After stirring for 3 hours, the mixture was left standing overnight. This reaction
Water was added to the mixture, extracted with chloroform and washed with saturated saline.
Clean and dry over anhydrous sodium sulfate, evaporate the solvent under reduced pressure.
Was. The obtained residue is subjected to silica gel column chromatography.
-(Eluent: benzene / ethyl acetate = 10/1)
As a result, 2.38 g of the target compound was obtained as a pale yellow oily substance.
It was obtained. [N_D ^{twenty two}= 1.5557,¹H-NM
R: δ _ppm ^CDCl3 5.24 (s, 2H), 6.70
(M, 1H), 7.25 (brs, 5H), 7.66
(D, J = 3Hz, 1H)]

Synthesis Example 2 Synthesis of 2-benzyl-4-bromo-5-trifluoromethoxy-3 (2H) -pyridazinone (Compound No. 2) 2-Benzyl-4-bromo-5-bromodifluoromethoxy- 1.1 g of 3 (2H) -pyridazinone was dissolved in 25 ml of anhydrous tetrahydrofuran, 1.1 g of silver tetrafluoroborate was added, and the mixture was stirred at reflux temperature for 21 hours under an argon atmosphere. After cooling, the insoluble matter was removed by filtration, and the solvent was distilled off under reduced pressure. The residue was collected by thin layer chromatography (silica gel, benzene) to give the desired compound 67
0 mg was obtained as an oil. n _D ²⁰ = 1.5486.

[Synthesis Example 3] 5-bromodifluoromethoxy-4-chloro-2- (4-methylbenzyl) -3
Synthesis of (2H) -pyridazinone (Compound No. 3). 5-bromodifluoromethoxy-4-chloro-3 (2
H) -Pyridazinone 250 mg was dissolved in N, N-dimethylformamide 8 ml, 4-methylbenzyl bromide 0.17 g and anhydrous potassium carbonate 0.2 g were added,
The mixture was stirred at room temperature for 24 hours. After distilling off the solvent under reduced pressure, the residue was extracted with ethyl acetate, washed with water and dried, and then the solvent was distilled off,
Purified by column chromatography (silica gel, benzene / ethyl acetate = 10/1), 200 mg of the target compound
I got Melting point 132.5-135.7 [deg.] C.

Synthesis Example 4 2-benzyl-5-bromodifluoromethoxy-4-n-butoxy-3 (2H)-
Synthesis of Pyridazinone (Compound No. 4) 1.5 g of 2-benzyl-4-bromo-5-bromodifluoromethoxy-3 (2H) -pyridazinone was dissolved in 30 ml of dehydrated benzene, and 0.3 g of n-butanol was added. . Then, 0.16 g of 55% sodium hydride was gradually added, and the mixture was heated with stirring at reflux temperature for 8 hours. After cooling
It was concentrated under reduced pressure and purified by column chromatography (silica gel, benzene) to obtain 1.03 g of the objective compound as an oily substance. n _D ²⁰ = 1.5341.

Table 1 shows examples of the compound of the present invention synthesized according to the scheme or the synthetic example and its physical properties, and examples of the compound of the present invention synthesized according to the scheme or the synthetic example. Is not limited by. The abbreviations in Table 1 have the following meanings.

Me: methyl group, Et: ethyl group, nP
r: normal propyl group, iPr: isopropyl group, n
Bu: normal butyl group, iBu: isobutyl group, sB
u: secondary butyl group, tBu: tertiary butyl group, nHex: normal hexyl group, Ph: phenyl group, mp: melting point (° C.), n _d ²⁰ = diffraction rate.

Table 1

[0027]

[Chemical 4]

[0028]

[Table 1] ────────────────────────────────── Compound No. R ¹ AB Physical Properties ───── ───────────────────────────── 5 Me Cl OCHF ₂ Oil 6 Me Cl OCBrF ₂ Oil 7 Et Cl OCBrF ₂ Oil 8 Et Cl OCF ₃ Oil 9 iPr Cl OCBrF ₂ Oil 10 iPr Cl OCF ₃ Oil 11 tBu Cl OCBrF ₂ Oil 12 tBu Cl OCF ₃ Oil 13 tBu H OCBrF ₂ Oil 14 tBu H OCF ₃ Oil 15 nHex F OCHF ₂ 16 PhCH ₂ H OCHF ₂ mp = 78.5-79.1 17 PhCH ₂ H OCBrF ₂ Oil 18 PhCH ₂ Cl OCBrF ₂ n _D ²⁰ = 1.5679 19 PhCH ₂ H OCF ₃ mp = 49.7-51.6 20 PhCH ₂ Cl OCF ₃ n _D ²⁰ = 1.5316 21 PhCH ₂ Br OCBrF ₂ n _D ²⁰ = 1.5820 22 PhCH ₂ Br OCF ₃ n _D ²⁰ = 1.5486 23 PhCH ₂ SMe OCBrF ₂ Oil 24 PhCH ₂ SOMe OCBrF ₂ Resin 25 PhCH ₂ SO ₂ Me OCBrF ₂ Resin 26 PhCH ₂ S-nPr OCBrF ₂ Oil 27 PhCH ₂ SnC ₁₂ H ₂₅ OCBrF ₂ Oil ───────────────────────────────────

[0029]

[Table 2] ────────────────────────────────── Compound No. R ¹ AB Physical Properties ───── ───────────────────────────── 28 PhCH ₂ SnC ₁₅ H ₃₁ OCHF ₂ 29 PhCH ₂ SPh OCBrF ₂ n _D ²⁰ = 1.6224 30 PhCH ₂ SOPh OCBrF ₂ 31 PhCH ₂ SO ₂ Ph OCClF ₂ 32 PhCH ₂ S (4-Cl-Ph) OCBrF ₂ mp = 93.6-95.2 33 PhCH ₂ OMe OCBrF ₂ n _D ²⁰ = 1.5540 34 PhCH ₂ OEt OCBrF ₂ n _D ²⁰ = 1.4178 35 PhCH ₂ O-iPr OCBrF ₂ n _D ²⁰ = 1.5354 36 PhCH ₂ O-nPr OCBrF ₂ n _D ²⁰ = 1.5388 37 PhCH ₂ O-nBu OCBrF ₂ n _D ²⁰ = 1.5341 38 PhCH ₂ OPh OCBrF ₂ n _D ²⁰ = 1.5859 39 PhCH ₂ OC ₂ H ₄ (4-Cl-Ph) OCBrF ₂ n _D ²⁰ = 1.5764 40 2-Cl-PhCH ₂ Cl OCBrF ₂ n _D ²⁰ = 1.5801 41 3-Cl-PhCH ₂ Cl OCBrF ₂ mp = 62.0-165.0 42 4-Cl-PhCH ₂ Cl OCBrF ₂ mp = 99.0-202.0 43 2-F-PhCH ₂ Br OCBrF ₂ n _D ²⁰ = 1.5663 44 3-F-PhCH ₂ Br OCBrF ₂ n _D ²⁰ = 1.5638 45 4-F-PhCH ₂ Br OCBrF ₂ mp = 71.8-72.6 46 2-F-PhCH ₂ Cl OCBrF ₂ n _D ²⁰ = 1.4420 47 3-F-PhCH ₂ Cl OCBrF ₂ n _D ²⁰ = 1.4216 48 4-F-PhCH ₂ Cl OCBrF ₂ mp = 51.8-53.1 49 2-Br-PhCH ₂ Cl OCBrF ₂ mp = 36.3-40.5 50 3-Br-PhCH ₂ Cl OCBrF ₂ ── ────────────────────────────────

[0030]

[Table 3] ────────────────────────────────── Compound No. R ¹ AB Physical Properties ───── ───────────────────────────── 51 4-Br-PhCH ₂ SnC ₁₅ H ₃₁ OCBrF ₂ 52 2-I-PhCH ₂ Cl OCBrF ₂ mp = 81.2-83.1 53 2-I-PhCH ₂ Br OCBrF ₂ mp = 80.0-80.6 54 2-I-PhCH ₂ SPh OCBrF ₂ n _D ²⁰ = 1.4460 55 3-Me-PhCH ₂ Cl OCBrF ₂ n _D ²⁰ = 1.5632 56 2-nBu-PhCH ₂ OC ₂ H ₄ Ph OCClF ₂ 57 4-Me-PhCH ₂ Cl OCBrF ₂ mp = 132.5-135.7 58 2-NO ₂ -PhCH ₂ Cl OCBrF ₂ mp = 64.0-68.3 59 2- Me-PhCH ₂ Cl OCBrF ₂ n _D ²⁰ = 1.3962 60 2-CF ₃ -PhCH ₂ Cl OCBrF ₂ n _D ²⁰ = 1.4208 61 3-CF ₃ -PhCH ₂ Cl OCBrF ₂ 62 3-CF ₃ -PhCH ₂ Cl OCBrF ₂ 63 2,6-Cl ₂ -PhCH ₂ Cl OCBrF ₂ mp = 87.9-91.2 64 2,6-F ₂ -PhCH ₂ Cl OCBrF ₂ mp = 58.9-60.2 65 2,6-F ₂ -PhCH ₂ Br OCBrF ₂ mp = 127.3-127.4 66 2,6-F ₂ -PhCH ₂ SPh OCBrF ₂ mp = 125.0-125.5 67 2,4-Cl ₂ -PhCH ₂ Cl OCBrF ₂ mp = 68.9-69.6 68 3,4-Cl ₂ -PhCH ₂ Cl OCBrF ₂ mp = 42.0-45.0 69 2,4,6-Cl ₃ -Ph Br OCBr F ₂ mp = 101.0-104.0 70 2,4,6-Cl ₃ -Ph Br OCF ₃ 71 PhCH ₂ CH ₂ Cl OCBrF ₂ n _D ²⁰ = 1.4284 72 PhCHMe Cl OCBrF ₂ n _D ²⁰ = 1.5507 73 PhCH ₂ OCH ₂ Ph OCBrF ₂ n _D ²⁰ = 1.5749 ───────────────────────────────────

[0031]

[Table 4] ────────────────────────────────── Compound No. R ¹ AB Physical Properties ───── ───────────────────────────── 75 2-pyridyl Cl OCBrF ₂ mp = 53.6-56.1 76 3-pyridyl Cl OCBrF ₂ 77 4 -pyridyl Cl OCF ₃ 78 CH ₂ = CHCH ₂ Cl OCBrF ₂ n _D ²⁰ = 1.4258 79 MeCH = CHCH ₂ Cl OCBrF ₂ Oil 80 CH ₂ = CMeCH ₂ Cl OCBrF ₂ Oil 81 Me ₂ C = CHCH ₂ Cl OCBrF ₂ 82 nPrCH = CHCH ₂ Cl OCBrF ₂ 83 PhCH ₂ CH ₂ Cl OCHF ₂ mp = 128.0-130.0 84 PhCHMe Cl OCHF ₂ Oil 85 MeCH = CHCH ₂ Cl OCHF ₂ mp = 38.0-40.0 86 PhCH = CHCH ₂ Cl OCBrF ₂ mp = 52.0- 55.0 87 PhCH = CHCH ₂ Cl OCF ₃ 88 3-Br-Ph Cl OCHF ₂ 89 4-I-Ph Cl OCHF ₂ 90 3-Cl-4-F-Ph Cl OCBrF ₂ 91 4-Cl-3-F-Ph Cl OCBrF ₂ 92 PhCH ₂ OCBrF ₂ H n _D ²⁰ = 1.5065 93 PhCH ₂ OCBrF ₂ Cl n _D ²⁰ = 1.5659 94 PhCH ₂ OCBrF ₂ OEt mp = 86.7-90.4 95 PhCH ₂ OCHF ₂ H 96 PhCH ₂ OCF ₃ Cl 97 Me OCBrF ₂ OEt ──────────────────────────── ─────

[0032]

[Table 5] ────────────────────────────────── Compound No. R ¹ AB Physical Properties ───── ───────────────────────────── 98 Et OCBrF ₂ H 99 tBu OCBrF ₂ Cl 100 CH ₂ = CHCH ₂ OCF ₃ OEt 101 MeCH = CHCH ₂ OCBrF ₂ H 102 CH ₂ = CMeCH ₂ OCBrF ₂ Cl 103 Me ₂ C = CHCH ₂ OCF ₃ OEt 104 2-Cl-PhCH ₂ OCBrF ₂ H 105 2-Cl-PhCH ₂ OCBrF ₂ Cl 106 2-Br- PhCH ₂ OCBrF ₂ H 107 2-CF ₃ -PhCH ₂ OCBrF ₂ Cl 108 2-I-PhCH ₂ OCBrF ₂ OEt ───────────────────────── ──────────

In applying the compound of the present invention as a pest control agent, generally, a suitable carrier, for example, a solid carrier such as clay, talc, bentonite, diatomaceous earth, white carbon or the like, water, alcohols (isopropanol,
Butanol, benzyl alcohol, furfuryl alcohol, etc.), aromatic hydrocarbons (toluene, xylene, etc.),
Ethers (anisole, etc.), ketones (cyclohexanone, isophorone, etc.), esters (butyl acetate, etc.),
It can be applied by mixing it with a liquid carrier such as acid amides (N-methylpyrrolidone etc.) or halogenated hydrocarbons (chlorobenzene etc.), and if desired, a surfactant, an emulsifier, a dispersant, a penetrant, a spreading agent. Glue, thickener, antifreeze,
It can be put to practical use in any dosage form such as a liquid agent, an emulsion, a wettable powder, a dry flowable agent, a flowable agent, a powder agent, and a granule by adding an anti-caking agent, a stabilizer and the like.

In addition, the compound of the present invention may be added to other kinds of herbicides, various insecticides, acaricides, or the like, during formulation or spraying, if necessary.
It may be mixed and applied with nematicides, fungicides, plant growth regulators, synergists, fertilizers, soil conditioners and the like. In particular, when mixed with other pesticides or plant hormones, it can be expected to reduce the amount of the applied drug, reduce the cost, broaden the insecticidal spectrum by the synergistic action of the mixed drugs, and have a higher pest control effect. At this time, it is possible to combine a plurality of known pesticides simultaneously. The types of pesticides used in combination with the compound of the present invention include, for example, Farm Chemicals Handbook (Farm Chemicals Handbo).
ok) Compounds described in the 1993 edition and the like.

The application dose of the compound of the present invention varies depending on the application scene, application time, application method, cultivated crop, etc., but generally it is 0.00 per hectare (ha) as an active ingredient amount.
About 5 to 50 kg is suitable. Next, specific examples of formulation of the preparation when the compound of the present invention is used are shown. However, the compounding examples of the present invention are not limited to these. In the following formulation examples, "part" means part by weight.

[Wettable powder] Compound of the present invention: 5 to 80 parts Solid carrier: 10 to 85 parts Surfactant: --- 1-10 parts Others --- 1-5 parts Other examples include anti-caking agents.

[Emulsion] Compound of the present invention: 1 to 30 parts Liquid carrier: 30 to 95 parts Surfactant: ..5 to 15 copies

[Flowable Agent] Compound of the present invention: 5 to 70 parts Liquid carrier: 15 to 65 parts Surfactant ... 5 to 12 parts Others ... 5 to 30 parts Others include, for example, antifreezing agents, thickeners and the like.

[Particulate wettable powder (dry flowable agent)] Compound of the present invention: 20 to 90 parts Solid carrier: 10 to 60 parts Surfactant・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1-20 copies

[Granule] Compound of the present invention: 0.1 to 10 parts Solid carrier: 90 to 99.99 parts Others:・ ・ ・ ・ ・ 1-5 copies

[Dust] Compound of the present invention: 0.01 to 30 parts Solid carrier: 67 to 99.5 parts Others: ··· 0 to 3 parts [Formulation Examples] Next, formulation examples of pest control agents containing the compound of the present invention as an active ingredient are shown, but the present invention is not limited thereto.

In the following formulation examples, "part" means part by weight.

[Formulation Example 1] Wettable powder Compound of the present invention: 50 parts Diklite PFP: 43 parts (Kaolin clay: Sikhlite Industry ( Trade name) Solpol 5050 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 2 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. product name) Lunox 1000C ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 3 parts ( Anionic surfactant: Toho Chemical Industry Co., Ltd. product name) Carplex # 80 (anti-caking agent) 2 parts (white carbon: Shionogi Pharmaceutical Co., Ltd. product name) The above is uniformly mixed and pulverized to obtain a wettable powder.

[Formulation Example 2] Emulsion Compound of the present invention: 3 parts Methylnaphthalene: 76 parts Isophorone: 15 Part Solpol 3005X ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 6 parts (mixture of nonionic surfactant and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) To do.

[Formulation Example 3] Flowable agent Compound of the present invention: 35 parts Agrisol S-711: 8 parts (Nonionic surfactant: Kao Trade name: Lunox 1000C: 0.5 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd .: trade name) 1% Rhodopol water ...・ ・ 20 parts (thickener: Loan Poulin's trade name) Ethylene glycol (antifreezing agent) ・ ・ ・ ・ ・ ・ ・ 8 parts ・ ・ ・ ・ ・ ・ ・・ ・ ・ 28.5 parts Mix evenly to make a flowable agent.

[Formulation Example 4] Granular wettable powder (dry flowable agent) Compound of the present invention: 75 parts Isoban No. 1: 10 parts (anion -Type surfactant: Kuraray Isoprene Chemical Co., Ltd. product name Vanillex N ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5 parts (Anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd. product name) Carplex # 80・ ・ ・ ・ ・ ・ ・ ・ 10 parts (White carbon: trade name of Shionogi Pharmaceutical Co., Ltd.) The above is uniformly mixed and pulverized to obtain a dry flowable agent.

[Formulation Example 5] Granules Compound of the present invention: 0.1 part Bentonite: 55.0 parts Talc: 44.9 parts After uniformly mixing and pulverizing the above, a small amount of water is added, and the mixture is kneaded by mixing with stirring, granulated by an extrusion granulator, and dried to give granules.

[Formulation Example 6] Dust formulation Compound of the present invention: 3.0 parts Carplex # 80: 0.5 part (white carbon: Yoshino Shiono Pharmaceuticals Co., Ltd. product name) Clay: 95 parts Diisopropyl phosphate: 1.5 parts The above ingredients are uniformly mixed and pulverized into a powder.

In use, the wettable powder, emulsion, flowable powder, and granular wettable powder are diluted 50 to 20000 times with water to contain the active ingredient in an amount of 0.005 to 1 hectare (ha).
Sprinkle so that it weighs 50 kg.

[Test Example] Next, the usefulness of the compound of the present invention as a pest control agent will be specifically described in the following test examples. Test Example 1 Insecticidal test against Cistanche salsa communis A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was tested) was diluted with water containing a spreading agent to give 500 ppm. A tomato leaf was soaked in this chemical solution for about 10 seconds, air-dried and placed in a Petri dish, and 10 second-instar larvae of the Nijuyahoushitentou larvae were released in the petri dish, and the lid was capped. Were stored in a thermostatic chamber at 25 ° C., and the mortality rate after 6 days was calculated from the following formula.
The test was conducted in a two-division system.

Mortality rate (%) = (number of dead insects / number of released insects) × 100 As a result, the following compounds showed a mortality rate of 80% or more. The compound of the present invention: No. 6,8,9,10,11,13,1
6,17,18,19,20,21,22,23,2
6,27,33,34,35,36,37,40,4
1, 42, 46, 47, 48, 59, 64, 67, 7
0,71,72,79,80,92,93,94

Test Example 2 Insecticidal test against brown planthopper 5% emulsion of the compound of the present invention described in the specification (25% wettable powder was used depending on the compound) was diluted with water containing a spreading agent to give a concentration of 500 ppm. Was prepared. A sufficient amount of this chemical solution was applied to the foliage of rice planted in a pot of 1 / 20,000 are. After air-drying, the cylinder was set up, 10 second-instar larvae of the brown planthopper were released per pot, and the lid was closed.
It was stored in a temperature-controlled room. The investigation was conducted after 6 days, and the mortality rate was calculated from the same formula as in Test Example 1. The test was conducted in a two-division system.

As a result, the following compounds showed a mortality of 80% or more. The compound of the present invention: No. 18, 20, 21, 22, 23, 2
6,29,33,35,38,40,47,48,4
9,52,55,59,60,64,67,70,7
9, 80, 92, 93

Test Example 3 Insecticidal test against green leafhoppers The foliage of rice in an emulsion of the compound of the present invention at a concentration of 500 ppm is immersed for about 10 seconds, and the foliage is placed in a glass cylinder to show resistance to organophosphorus insecticides. Release adult worms, cover them with holes, and store them in a thermostatic chamber at 25 ° C.
The number of dead insects after the day was examined, and the death rate was calculated from the same formula as in Test Example 1. The test was conducted in a two-district system. As a result, the following compounds showed a mortality of 80% or more.

Compound of the present invention: No. 18, 19, 20, 2
1, 22, 23, 26, 27, 29, 32, 35, 3
8, 42, 43, 44, 45, 46, 47, 48, 4
9,55,60,64,67,70,72,75,7
8, 79, 80, 86, 92, 93

Test Example 4 Insecticidal test against diamondback moth (Konaga moth) A kanlan leaf was immersed in a water-emulsion solution of the compound of the present invention at a concentration of 500 ppm for about 10 seconds, air-dried, and placed in a petri dish, and the second-instar larva of the diamondback moth was put into the petri dish. Release 10 each
It was put in a thermostatic chamber at 25 ° C. with a lid having a hole, and the number of dead insects was examined 6 days later, and the dead insect rate was calculated from the same formula as in Test Example 1. The test was conducted in a two-district system. As a result, the following compounds showed a mortality of 80% or more. The compound of the present invention: No. 22, 45, 53, 79, 80

Test Example 5 Acaricidal efficacy test against Nite spider Mite The leaf of kidney bean was cut into a circle with a diameter of 3.0 cm using a leaf punch and placed on a damp filter paper on a styrene cup having a diameter of 7 cm. Add 1 larvae of the spider mite to each leaf
0 animals were inoculated. 5% of the compound of the invention described in the description
An emulsion (25% wettable powder depending on the compound) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 1000 ppm, and 2 mL of this chemical solution was sprayed per styrene cup using a rotary spraying tower. And store it in a thermostatic chamber at 25 ° C for 9
The mortality rate after 6 hours was calculated from the same formula as in Test Example 1. The test was conducted in a two-division system. As a result, the following compounds showed a mortality of 80% or more.

Compound of the present invention: No. 6,7,8,9,1
0,11,17,18,19,20,21,22,2
3,24,26,27,29,32,34,38,3
9,40,41,42,43,44,45,46,4
7, 48, 49, 52, 53, 54, 55, 58, 5
9, 60, 63, 64, 65, 67, 68, 69, 7
0,71,72,75,79,84,86,92,9
3,94

[0059]

INDUSTRIAL APPLICABILITY The compound of the present invention has excellent insecticidal and acaricidal activity against many agricultural pests and spider mites, and has almost no adverse effect on mammals, fish and beneficial insects. Therefore, the compound of the present invention can provide a useful pest control agent.

Front page continued (72) Inventor Rika Miyaji 1 722, Tsuboi-cho, Funabashi-shi, Chiba Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Inventor Toshiaki Takeyama 1 722, Tsuboi-cho, Funabashi, Chiba Nissan Chemical Industry Co., Ltd. Company Central Research Laboratory (72) Inventor Toshiro Miyake 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Nissan Chemical Industry Co., Ltd.Biological Sciences Research Institute (72) Inventor Akihiko Fujita 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama 1470 Nissan Kagaku Kogyo Institute of Biological Sciences, Inc. (72) Inventor Yoichi Inoue 1470, Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Nissan Chemical Industry Co., Ltd.Institute of Biological Sciences (72) Inventor Norihiko Mimori 722, Tsuboi-cho, Funabashi-shi, Chiba Nissan Chemical Central Research Institute, Kogyo Co., Ltd.

Claims (5)

[Claims] 1. Formula (1):[In the formula, R¹Is C_1-6Alkyl group, C_3-6Alkenyl
Group, phenethyl group, cinnamyl group, pyridylmethyl group,
Phenyl group substituted by halogen atom, or C _1-4A
Rukiru group, C_1-4Haloalkyl group, nitro group or ha
Substituted with a phenyl group, which may be substituted with a rogen atom
Represents a methyl group represented by R²Is a hydrogen atom, a halogen atom, C_1-6Alkoxy
Group, C_1-15Alkylsulfenyl group, C_1-15Alkyls
Rufilnyl group, C_1-15Alkylsulfonyl group, halogen
Phenylsulfenyl optionally substituted with a nitrogen atom
Group, phenylsulfur optionally substituted with a halogen atom
Finyl group, a phenyl group which may be substituted with a halogen atom.
Nylsulfonyl group, benzyloxy group, phenoxy group
Or a phenethyl group optionally substituted with a halogen atom
Represents R³Represents a methyl group substituted with a halogen atom. ]
A 3 (2H) -pyridazinone derivative represented by: 2. The 3 (2H) -pyridazinone derivative according to claim 1, wherein R ³ is a trifluoromethyl group, a difluoromethyl group or a bromodifluoromethyl group. 3. R ² is bonded to the 4-position of the pyridazinone ring and R ³ is bonded to the 5-position of the pyridazinone ring.
The described 3 (2H) -pyridazinone derivative. 4. The method according to claim ² , wherein R ² is a hydrogen atom, a halogen atom or a C _1-6 alkoxy group, and is bonded to the 5-position of the pyridazinone ring, and R ³ is bonded to the 4-position of the pyridazinone ring. 3 (2H) -pyridazinone derivative of 5. A pest control agent comprising one or more 3 (2H) -pyridazinone derivatives according to claim 1 as an active ingredient.