JPH0525141A - Pyridazinone derivative and vermin-controlling agent - Google Patents

Abstract

PURPOSE:To provide a new 3(2H)-pyridazinone derivative having excellent vermin-controlling activity. CONSTITUTION:The 3(2H)-pyridazinone derivative of formula 1 [Ar is (halogenated or haloalkylated) phenyl; R<1> is 1-4C alkyl; R<2> is 1-4C alkyl, (substituted)phenyl, 1-4C alkoxy, (substituted)phenoxy, COR<3> (R<3> is 1-4C alkoxy) or NR<4>R<5> (R<4> and R<5> are 1-4C alkyl or R<4> and R<5> together form a ring or an alkylene chain which may be interrupted by O or NCH3)], e.g. 2- benzyl-5-[2-(N-methoxyoxalyl-N-ethoxycarbonylamino)ethoxy]-3(2H)-pyrid azinone. The compound of formula 1 can be produced e.g. by reacting a compound of formula 3 (Z<1> is halogen or OH) with a compound of formula 4 (Z<2> is OH when Z<1> is halogen, or Z<2> is halogen when Z<1> is OH) and reacting the obtained compound of formula 5 with a proper acid halide.

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]

The following patents are related to the present invention. European patent publication 0088384 European patent publication 0134439 European patent publication 0183212 European patent publication 0199281 European patent publication 0210647 European patent publication 0193853 European patent publication 0232825 European patent publication 0302346 Known compounds contained in these patents Is the general formula
It is represented by (2).

[0003]

[Chemical 2]

The characteristics of these patents are, for example, European Patent Publication No. 0088384, European Patent Publication No. 0134439,
European Patent Publication 0183212, European Patent Publication 019
In 9281 and European Patent Publication No. 0232825, Y'is an oxygen atom or a sulfur atom, but A'is characterized by being a substituent such as halogen, and in European Patent Publication No. 0210647, R'is an aryl group. It is characterized in that in European Patent Publication No. 0302346, R '
Is a substituent such as an alkyl group substituted with a halogen atom. European Patent Publication 0193853
In the issue, Y'is a nitrogen atom or an oxygen atom, but A '
Is a substituent such as halogen. The compounds of the present invention are new compounds not included in these prior art.

[0005]

SUMMARY OF THE INVENTION The present invention is to provide a novel compound and an insecticide having excellent insecticidal activity.

[0006]

The present invention is based on the general formula (1)

[0007]

[Chemical 3]

[In the formula, Ar represents a phenyl group which may be substituted with a halogen atom or a haloalkyl group, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms. group, optionally substituted phenyl group, an alkoxy group having 1 to 4 carbon atoms, optionally substituted phenoxy group, an -COR ³ or -NR ⁴ R ^5, R ³ is from 1 to 4 carbon atoms Represents an alkoxy group,
R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 4 carbon atoms, or R ⁴ and R ⁵ are taken together to form a ring,
The oxygen atom or -NCH ₃ - represents an alkylene chain optionally interrupted by. ] 3 (2
The present invention relates to a H) -pyridazinone derivative and a pest control agent containing one or more of the derivatives as an active ingredient.

The present inventors have found that the compound of the present invention represented by the general formula (1) has an excellent pest control action. For example, a known compound group represented by the general formula (2) has strong insecticidal, acaricidal, nematicidal, and bactericidal activity, has a broad insecticidal spectrum, and is excellent in fast-acting properties. , It is slow-acting because it has the effect of inhibiting the transformation of harmful insects.

Further, the compound of the present invention is effective against various harmful pests at an extremely low drug concentration. Examples of the insect pests include the agricultural insect pest leafhoppers, the brown planthopper, the green peach aphid, the diamondback moth, Plutella xylostella, Nami mites, citrus spider mites, Kanzawa mites, locust grasshoppers, and scabbard grasshoppers.
Housefly, chironomid, German cockroach, ants, fleas,
Lice and other stored-product insects
Examples include house pests such as termites such as striped moth, etc., livestock pests such as ticks, fleas, lice, flies, indoor dust mites such as mites, leopard mites and claw mites, and mollusc slugs and snails.

That is, Orthoptera, Termites, Hemiptera,
It was found that it can be effectively controlled against Lepidoptera, Coleoptera, Hymenoptera, Diptera, mites and lice. This effect was specifically described in the biological test example described later. The compound of the present invention can be produced by a number of methods. These methods are as follows, for example.

[0012]

[Chemical 4]

[0013]

[Chemical 5]

Ar and R in (A method) and (B method)
¹ and R ² are as defined above, Z ¹ represents a halogen atom or a hydroxyl group, Z ² represents a hydroxyl group when Z ¹ is a halogen atom, when Z ¹ is a hydroxyl group is a halogen atom, methane Represents a sulfonyloxy group. More specifically, (Method A) is a method of reacting a compound represented by the general formula (3) with a compound represented by the general formula (4) in the presence of a base in a suitable solvent. It means that the compound of the present invention (1) can be produced by producing a compound represented by the formula (1) and further reacting the compound represented by the general formula (5) with an acid halide in the presence of a base in an appropriate solvent. Examples of the solvent include ethers such as N, N-dimethylformamide, acetonitrile and tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane, aromatic hydrocarbons such as benzene and toluene, and toluene-water. A mixed solvent of
As the base, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, organic bases such as triethylamine, pyridine and 4-N, N-dimethylaminopyridine are preferable, and tetra-n-butylammonium bromide and the like are preferable. Good results may be obtained in some cases by adding a quaternary ammonium salt as a catalyst.

In Method (B), the compound of the present invention (1) is prepared by reacting the compound of the general formula (6) with the compound of the general formula (7) in the presence of a base in a suitable solvent.
Indicates that can be manufactured. As the solvent, ethers such as N, N-dimethylformamide, acetonitrile and tetrahydrofuran, ketones such as methyl ethyl ketone,
Aromatic hydrocarbons such as benzene and toluene, and a mixed solvent of toluene-water are preferable, and examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine and pyridine. Is preferable, and good results may be obtained by adding a quaternary ammonium salt such as tetraammonium bromide as a catalyst.

[0016]

EXAMPLES The production method of the compound of the present invention will be described with reference to specific production examples, but the compound of the present invention is not limited thereto. Production Example 1 2-benzyl-5- {2- (N-methoxyoxalyl-
N-ethoxycarbonylamino) ethoxy} -3 (2
H) -Pyridazinone (Compound No. 25) Preparation 2-benzyl-5- (2-ethoxycarbonylamino)
Ethoxy-3 (2H) -pyridazinone 1.5 g and 4-
To a solution of 0.05 g of dimethylaminopyridine in 10 ml of 1,2-dichloroethane, a solution of 1.16 g of methoxallyl chloride in 2 ml of 1,2-dichloroethane was slowly added dropwise at 80 ° C. with stirring. The mixture was then stirred at 80 ° C overnight. After allowing to cool, the reaction mixture was diluted with dichloromethane, washed successively with 5% aqueous sodium hydrogen carbonate solution, 5% hydrochloric acid, water and saturated brine, and dried over sodium sulfate. The residue obtained by completely removing the organic solvent by vacuum distillation was subjected to column chromatography (silica gel, solvent
Purification with ethyl acetate: benzene = 1: 1) gave 0.1 g of the desired compound (melting point 112-116 ° C.) as white crystals. Production Example 2 2-benzyl-5- {2- (N-ethoxyoxalyl-
N-ethoxycarbonylamino) ethoxy} -3 (2
H) -Pyridazinone (Compound No. 27) Preparation 2-benzyl-5- (2-ethoxycarbonylamino)
Ethoxy-3 (2H) -pyridazinone 1.5 g and 4-
To a solution of 0.05 g of dimethylaminopyridine in 10 ml of 1,2-dichloroethane, 1.3 g of etoxalyl chloride
A solution of 2-dichloroethane (2 ml) was slowly added dropwise at 80 ° C with stirring. The mixture was then stirred at 80 ° C. for 20 hours. After allowing to cool, the reaction mixture was diluted with dichloromethane and added to 5
% Aqueous sodium hydrogen carbonate solution, 5% hydrochloric acid, water and saturated brine successively, and dried over sodium sulfate. The residue obtained by completely removing the organic solvent by vacuum distillation was recrystallized from ethanol-normal hexane to obtain 1.07 g of the desired compound (melting point: 81 to 82 ° C) as white crystals.

The compounds included in the present invention include, for example, the compounds shown in Table 1. However, the compounds in Table 1 are for exemplification, and the present invention is not limited to these. In the table, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ph is a phenyl group, i- is iso, s is secondary, and t is tertiary. Represent

[0018]

[Chemical 6]

[Table 1]

────────────────────────────── No. Ar R ¹ R ² ─────────── ──────────────────── 1 Ph Me Me 2 Ph Me Et 3 Ph Me Pr 4 Ph Me Bu 5 Ph Me Ph 6 Ph Me OMe 7 Ph Me OEt 8 Ph Me OPh 9 Ph Me CO ₂ Me 10 Ph Me CO ₂ Et 11 Ph Me CO ₂ Pr-i 12 Ph Me NMe ₂ 13 3-FC ₆ H ₄ Me CO ₂ Et 14 Ph Et Me 15 Ph Et Et 16 Ph Et Bu -t 17 Ph Et Ph 18 Ph Et OMe 19 3-FC ₆ H ₄ Et OMe 20 3-Cl-C ₆ H ₄ Et OMe ───────────────────── ──────────

Table 1 continued ────────────────────────────── No. Ar R ¹ R ² ─────── ──────────────────────── 21 Ph Et OEt 22 3-FC ₆ H ₄ Et OEt 23 Ph Et OBu-s 24 Ph Et OPh 25 Ph Et CO ₂ Me 26 3-FC ₆ H ₄ Et CO ₂ Me 27 Ph Et CO ₂ Et 28 3-FC ₆ H ₄ Et CO ₂ Et 29 3-Cl-C ₆ H ₄ Et CO ₂ Et 30 3-CF _3- C ₆ H ₄ Et CO ₂ Et 31 3-Br-C ₆ H ₄ Et CO ₂ Et 32 3,5-F ₂ -C ₆ H ₃ Et CO ₂ Et 33 3,5-Cl ₂ -C ₆ H ₃ Et CO ₂ Et 34 2,4-F ₂ -C ₆ H ₃ Et CO ₂ Et 35 4-FC ₆ H ₄ Et CO ₂ Pr 36 Ph Et CO ₂ Ph 37 Ph Et NMe ₂ 38 3-FC ₆ H ₄ Et NMe ₂ 39 Ph Et NEt ₂ 40 Ph Et 4-morphorinyl 41 Ph Et 4-Me-1-piperazinyl 42 Ph Pr Pr-i ─────────────────────── ────────

Table 1 continued ────────────────────────────── No. Ar R ¹ R ² ─────── ──────────────────────── 43 Ph Pr CO ₂ Me 44 Ph Pr CO ₂ Et 45 Ph Pr-i CO ₂ Et 46 Ph Bu CO ₂ Me 47 Ph Bu CO ₂ Et 48 Ph Bu-i NMe ₂ 49 Ph Et 1-pyrrolidinyl 50 Ph Et 1-piperidinyl ───────────────────────── When the compound of the present invention is used as a pest control agent, generally, a suitable carrier, for example, solid carrier such as clay, talc, bentonite, diatomaceous earth or the like, water, alcohols (methanol, ethanol, etc.), aromatic Liquids such as hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.) It can be mixed with a carrier and applied, and if desired, an emulsifier, a dispersant, a suspending agent, a penetrating agent, a spreading agent, a stabilizer, etc. are added, and an emulsion, an oil, a wettable powder, a powder, a granule, a flowable It can be put to practical use in any dosage form such as a drug. Moreover, you may mix-apply with another type of herbicide, various insecticides, a bactericide, a plant growth regulator, a synergist, etc. at the time of formulation or spraying as needed. The application dose of the compound of the present invention varies depending on the application scene, application time, application method, target pests, cultivated crops, etc., but is generally 0.005 per hectare as the active ingredient amount.
About 50kg is suitable.

Next, the compounding ratios and types of various preparations of the present invention will be described below.

[0023]

[Table 2] ───────────────────────────────────               Active Ingredient Carrier Surfactant Other ingredients (auxiliaries) ───────────────────────────────────   Emulsion 1 to 25 52 to 95 3 to 20 0 to 20   Oil 1-30 70-99   Flowable 1-70 10-90 1-200-10   Wettable powder 1-70 15-93 3-10 0-5   Powder 0.01 to 30 67 to 99.5 0 to 3   Granules 0.01 to 30 67 to 99.5 0 to 8   Granular wettable powder 1-90 5-90 1-50 0-30 ───────────────────────────────────   The numerical values in the above table represent% by weight.

In use, emulsions, oils, flowables, wettable powders and granular wettable powders are diluted with a predetermined amount of water and then sprayed, while powders and granules are directly sprayed without being diluted with water. . The granules also include bait agents. Next, examples of each component in each of the above formulations will be given. Emulsion Active ingredient: Carrier of the present invention: Xylene, dimethylformamide, methylnaphthalene, cyclohexanone, dichlorobenzene, isophorone Surfactant: Solpol 2680, Solpol 3005X, Solpol 3353 Other ingredients: Piperonyl butoxide , Benzotriazole oil Active ingredient: Compound of the present invention carrier: Xylene, Methylcellosolve, Kerosene Flowable active ingredient: Compound carrier of the present invention: Water surfactant: Lenox 1000C, Solpol 3353, Soprofer FL, Nipol, Agrisol S-710 , Sodium lignin sulfonate Other ingredients: Zansan gum, formalin, ethylene glycol, propylene glycol wettable powder Active ingredient: Compound carrier of the present invention: Calcium carbonate, kaolinite, Sieglite D, Sieglite PFP, diatomaceous earth, talc surfactant Agents: Solpol 5039, Lunox 1000C, Lignin Calcium Sulfate, Sodium Dodecylbenzene Sulfonate, Solpol 5050, Solpol 005D, Solpol 5029-O Other Ingredients: Carplex # 80 Powder Active Ingredient: Compound of the Invention Carrier: Calcium Carbonate, Kaori Knight, Sikhlite D, talc Other ingredients: diisopropyl phosphate, Carplex # 80 granules (1) Active ingredient: Compound of the present invention carrier: calcium carbonate, kaolinite, bentonite, talc Other ingredients: calcium lignin sulfonate, poly Vinyl Alcohol Granules (2) [Bait] Active Ingredient: Compound of the Invention Carrier: Wheat Flour, Bran, Corn Grit, Zykrite D Other Ingredients: Paraffin, Soybean Oil Granules Active Ingredient: Compound Carrier of the Invention: Calcium carbonate, kaolinite, Chlorite, clay, ammonium sulfate, urea, white carbon Surfactant: Lunox 1000C, formalin condensate of naphthalene sulfonic acid, polyoxyethylene-nonyl phenyl ether, sodium lignin sulfonate Other components: Epoxidized soybean oil, antioxidant, etc. The following are formulation examples of pest control agents containing the compound of the present invention as an active ingredient, but the present invention is not limited thereto. In addition,
In the following formulation examples, "part" means part by weight. Formulation Example 1 Emulsion Compound of the present invention -------- 5 parts xylene -------- 70 parts N, N-dimethylformamide ------- 20 parts Solpol 2680 ---- ----- 5 parts [mixture of nonionic surfactant and anionic surfactant: trade name of Toho Kagaku Kogyo Co., Ltd.] The above components are uniformly mixed to form an emulsion. At the time of use, the above emulsion is diluted 50 to 20000 times and sprayed so that the amount of active ingredient is 0.005 to 50 kg per hectare. Formulation Example 2 Wettable powder Compound of the present invention -------- 25 parts Sikhlite PFP -------- 66 parts [mixture of kaolinite and sericite; Sikhlite Industry Co., Ltd. trade name] Solpol 5039 ------- 4 parts [Anionic surfactant: Toho Chemical Industry Co., Ltd. product name] Carplex # 80 ------- 3 parts [White carbon: Shionogi & Co., Ltd. Trade name] Calcium lignin sulfonate ------- 2 parts or more are uniformly mixed and pulverized to obtain a wettable powder. At the time of use, the wettable powder is diluted 50 to 20000 times and sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare. Formulation Example 3 Oil agent Compound of the present invention -------- 10 parts methyl cellosolve -------- 90 parts or more are uniformly mixed to obtain an oil agent. At the time of use, the above oil agent is sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare. Formulation Example 4 Powder Compound of the present invention ------- 3.0 parts Carplex # 80 ------- 0.5 part [White carbon: Shionogi Pharmaceutical Co., Ltd. product name] Clay ------ -95 parts Diisopropyl phosphate ------- 1.5 parts or more are uniformly mixed and pulverized to give a powder. At the time of use, the above powder is sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare. Formulation Example 5 granules Compound of the present invention ------- 5 parts Bentonite ------- 54 parts Talc ------- 40 parts Calcium lignin sulfonate ------- 1 part The above is uniformly mixed and pulverized, a small amount of water is added, and the mixture is stirred and mixed, granulated by an extrusion granulator, and dried to obtain granules. When using the above granules, the amount of active ingredient is 0.0 per hectare.
Sprinkle so that it becomes 05 to 50 kg. Formulation Example 6 Flowable agent Compound of the present invention ------- 35 parts Solpol 3353 ------- 10 parts [Nonionic surfactant: Toho Chemical Industry Co., Ltd. trade name] Lunox 1000C --- ---- 0.5 part [Anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.] 1% aqueous solution of xanthan gum (natural polymer) ------- 20 parts water ------- 34.5 parts The above components except the active ingredient (the compound of the present invention) are uniformly dissolved, and then the compound of the present invention is added and well stirred, followed by wet grinding with a sand mill to obtain a flowable agent. At the time of use, the flowable agent is diluted 50 to 20000 times and sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare. Formulation Example 7 Granular wettable powder compound of the present invention -------- 50 parts clay -------- 10 parts ammonium sulfate -------- 20 parts sodium lignin sulfonate ---- ---- 10 parts formalin condensate of naphthalene sulfonic acid --- 10 parts or more uniformly mixed and pulverized, and added with water and kneaded
Granulate with an extrusion granulator equipped with a 0.5 mmφ screen and dry the water to obtain a granular wettable powder. At the time of use, the amount of the above-mentioned granular wettable powder was 0.005 per hectare.
Sprinkle so that it is ~ 50kg.

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 green leafhopper 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was used) was diluted with water containing a spreading agent, and a chemical solution having a concentration of 500 ppm was diluted. Adjusted to. 1/2000 this chemical
0 Sprinkle a sufficient amount on the foliage of the rice planted in the Earl pot,
After air-drying, 20 second-instar larvae of the leafhopper leafhopper, which is resistant to organophosphorus insecticides and carbamate insecticides, were released in 20 pots per pot, and the rice was covered with a wire cage cylinder cage and stored in a temperature-controlled room.

The survey was conducted 30 days later, and the number of parasites (number of surviving insects) of green leafhoppers parasitic on each rice was investigated.
Was investigated and the mortality rate was calculated by the following formula. In addition,
The test was repeated twice in one section. Mortality rate (%) = (1-number of surviving worms / number of worms) × 100 As a result, the following compounds showed a high effect of mortality rate of 100%.

Compound of the present invention No .: 27. Test Example 2 Insecticidal test against brown planthopper The same procedure as in Test Example 1 was repeated except that the 2nd instar larva of the brown planthopper was used in place of the 2nd instar larva of the leafhopper leafhopper, which is resistant to organophosphorus insecticides and carbamate insecticides. It was

As a result, the following compounds had a mortality rate of 100.
% Showed a high effect. Inventive compound No .: 25, 27. Test Example 3 Insecticidal test against Tricholoma communis A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder or 20% oil solution was used depending on the compound) was used.
Acetone was added to the transparent pitch tube to obtain acetone solution having a concentration of 500 ppm.

10 cc of this acetone solution was added to 10 g of wheat flour put in a petri dish having a diameter of 9 cm, and the mixture was stirred and then acetone was distilled off. Then, 10 adult male and female Konosutomodoki were released into this petri dish and stored in a temperature-controlled room. The survey was carried out 90 days later, and the number of emerged adult adults was observed. The test was repeated twice in one section. As a result, the following compounds did not show any newly emerged adults.

Compounds of the present invention No .: 25, 27. Test Example 4 Insecticidal test against Spodoptera litura A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder or 20% oil depending on the compound was tested) was weighed in a transparent spitch tube, and acetone was added. As a result, an acetone solution having a concentration of 500 ppm was obtained.

10 cc of this acetone solution was added to 10 g of rice bran placed in a petri dish having a diameter of 9 cm, and after stirring, acetone was distilled off. Then, 10 larvae of Spodoptera litura moth were released on this petri dish and stored in a temperature-controlled room. Survey 3
The test was performed after 0 days and the number of emerged adults was observed. The test was repeated twice in one section. As a result, the following compounds did not show any newly emerged adults.

Compounds of the present invention No .: 25, 27. Test Example 5 Insecticidal test against diamondback moth A 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 prepare a solution having a concentration of 500 ppm. Adjusted to a chemical solution. Soak citrus leaves in this chemical solution, air-dry, and put in a petri dish with a diameter of 7 cm.
10 3rd instar larvae of diamondback moth were released per petri dish and stored in a temperature-controlled room.

The examination was carried out 20 days later, and the number of emerged adults (the number of surviving insects) was examined, and the mortality rate was calculated by the same formula as in Test Example 1. The test was repeated twice in one section. As a result, the following compounds showed a high effect with a mortality of 100%. Inventive compound No .: 25, 27.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiyuki Umehara             1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Nissan             Chemical Industry Co., Ltd. (72) Inventor Toshiro Miyake             1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Nissan             Chemical Industry Co., Ltd. (72) Inventor Hiroshi Haruyama             1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Nissan             Chemical Industry Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): [In the formula, Ar represents a phenyl group which may be substituted with a halogen atom or a haloalkyl group, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ² represents 1 to 4 carbon atoms.
Alkyl, optionally substituted phenyl group, an alkoxy group having 1 to 4 carbon atoms, optionally substituted phenoxy group, an -COR ³ or -NR ⁴ R ^5, R ³ is 1 to carbon atoms Or R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 4 carbon atoms or R 4
⁴ and R ⁵ together form a ring and represent an alkylene chain which may be interrupted by an oxygen atom or —NCH ₃ —. ] The 3 (2H) -pyridazinone derivative represented by these. 2. A pest control agent containing one or more 3 (2H) -pyridazinone derivatives according to claim 1 as an active ingredient.