JPS63159374A - Pyridazinone derivative and insecticide, acaricide and nematocide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is 1-6C alkyl; A is halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio or H; X is O or S; R<1>-R<4> are H or 1-4C alkyl; m is 0 or 1; Q is formula II, V, VI, etc.; Y is each group in A except H, NO2 or 1-4C alkylsulfonyl; n is 0, 1 or 2; Z is 1-9C alkyl, 2-8C alkenyl, 1-9C haloalkyl, 1-6C haloalkoxy, etc.). EXAMPLE:2-tert-Butyl-4-chloro-5-(4-pivaloylbenzylthio)-3(2H)-pyridazin one. USE:An agricultural and horticultural insecticide, acaricide, nematocide and expellent against mites parasitic on animals. PREPARATION:A compound expressed by formula III is reacted with a compound expressed by formula IV (either one of X<1> and X<2> is halogen and the other is OH or SH) in the presence of a hydrogen halide absorbent in a solvent without affecting the reaction to afford the aimed compound expressed by formula I.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides novel 3(2H)-pyridazinone derivatives and insecticides for agricultural and horticultural use, acaricides, nematicides and parasitic animals containing the derivatives as active ingredients. This relates to a tick repellent.

[Conventional technology]

The present inventors previously discovered that some 3(2H)-pyridazinone derivatives represented by the following general formula (n) have insecticidal, acaricidal, nematicidal, and bactericidal effects for agricultural and horticultural purposes. . (Refer to European Published Patent No. 0088384, European Published Patent No. 0134439, and European Published Patent No. 0183212) 1ze0 [In the formula, for example, R' is an alkyl group, A' is a halogen atom, R'l and R8 is a hydrogen atom or a lower alkyl group,
X' represents an oxygen atom or a sulfur atom, and Y' represents a lower alkyl group, a cycloalkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a substituted phenyl group, or the like. ] The compound of the present invention represented by the general formula (1) described below is a novel compound not included in the prior art represented by the general formula (n), and has excellent insecticidal, acaricidal, and nematocidal effects, The present invention was completed based on the discovery that organisms harmful to agriculture and horticulture can be effectively controlled. This effect will be clearly demonstrated in the test examples described later.

[Aspects of the invention]

The present invention is based on the general formula [I]: [wherein, R represents an alkyl group having 1 to 6 carbon atoms, and A represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms]
represents an alkoxy group, an alkylthio group having 1 to 4 carbon atoms, or a hydrogen atom, X represents an oxygen atom or a sulfur atom, and Rl, RZ, R3, and R' each independently represent a hydrogen atom or a represents a lower alkyl group of
m is 0 or 1 to 4 alkyl group, alkoxy group having 1 to 4 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, nitro group,
represents an alkylthio group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms, n represents 0.1 or 2, and Z is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 8 carbon atoms; group, haloalkyl group having 1 to 9 carbon atoms, 1 carbon number
-6 haloalkoxy group, C2-4 alkenyloxy group, C2-4 alkynyloxy group, C1
represents an integer of alkyl of ~4, R5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms,
3(
The present invention relates to a 2H)-pyridazinone derivative and an insecticide for agricultural and horticultural use, an acaricide, a nematicide, and a repellent for mites parasitic on animals, which contain the derivative as an active ingredient.

Specific examples of the compounds included in the present invention include the compounds shown in Tables 1 and 2. however,
The compounds shown in Tables 1 and 2 are for illustrative purposes only, and the present invention is not limited thereto. [However, in Tables 1 and 2, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, [ is tertiary, S is secondary, i
indicates iso. ] Among the compounds included in the present invention, in the case of a compound having an asymmetric carbon atom, the (+) and (-) forms of optically active compounds are also included.

The compound numbers shown in Tables 1 and 2 are referred to in the production examples, formulation examples, and test examples described later.

[Margin below]

Table 1 (hereinafter referred to as margins) Table 2 (hereinafter referred to as margins) 01 to G23 in Table 2 are groups represented by the following structural formulas.

The compound of the present invention can be produced according to the following reaction formula.

(1) (IV) Compound (1) of the present invention [wherein R, R', R'', R3, R', A, Q.

Z and m represent the same meanings as above, Xl represents a halogen atom, -011 or -5i, and X2 represents a halogen atom, -011 or -511. However, when XI is a halogen atom, X2 represents -OH or -SH, and X2
When is -011 or -SH, X2 represents a halogen atom. ] That is, the compound (1) of the present invention consists of a 3(2)1)-pyridazinone derivative represented by the above formula (III), which is one of the raw materials, and a 3(2)1)-pyridazinone derivative represented by the above formula (IV), which is the other raw material. It can be produced by reacting a compound with a hydrogen halide absorbent in a solvent that does not affect the reaction.
Ru. In the present invention, solvents include lower alcohols (e.g. methanol, ethanol, etc.), ketones (e.g.
acetone, methyl ethyl ketone, etc.), hydrocarbons (e.g., benzene, toluene, etc.), ethers (e.g., isopropyl ether, tetrahydrofuran, 1°4-dioxane, etc.), amides (e.g., N,N-dimethylformamide, hexamethyl Phosphoric triamide, etc.), halogenated hydrocarbons (eg, dichloromethane, dichloroethane, etc.) can be used. A mixed solvent of these solvents and water can also be used if necessary.

Hydrogen halide absorbers include inorganic bases (e.g., sodium hydride, sodium hydroxide, potassium hydroxide,
Sodium carbonate, potassium carbonate, hydrogen carbonate, etc.) and organic bases (eg, sodium methoxide, sodium ethoxide, triethylamine, pyridine, etc.) can be used. Also, if necessary,
A tetraammonium salt (e.g., tetra-n-
butylammonium bromide, triethylbenzylammonium chloride, etc.) may be added as a catalyst. The reaction temperature can range from room temperature to the boiling point of the solvent used in the reaction.

Although the molar ratio of the raw materials can be set arbitrarily, it is advantageous to carry out the reaction at an equimolar ratio or a ratio close to it.

Next, the method for producing the compound of the present invention will be explained with specific production examples, but the present invention is not limited to these.

! ! lLL 2-t-butyl-4-chloro-5-(4
-pivaloylbenzylthio)-3 (2H)-Synthesis of pyridazinone (compound level 40) 2-t-butyl-4-chloro-5-mercapto-3(2
H)-pyridazinone (1,09 g) and 4-pivaloylbenzyl bromide (1,28 g) were dissolved in N,N-dimethylformamide (10 ml), and sodium carbonate (0,53 g) was added thereto at room temperature for 18 hours. This ?8 liquid was poured into water and extracted with benzene, washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the obtained crystals were recrystallized from hexane-ethanol. thing(
1.83 g) was obtained.

Melting point: 139.8-143.1°C Synthesis of 14-chloro-2-ethyl-5-(4-isobutyrylbenzyloxy)-3 (2H)-pyridazinone (compound t'h33) 4-chloro- 2-ethyl-5-hydroxy-3(2H)
-Pyridazinone (0,87 g) and 4-isobutyrylbenzyl bromide (1,21 g) were dissolved in N,N-dimethylformamide (10 nl), and sodium carbonate (
0.53 g) was added thereto, and the mixture was stirred at room temperature for 18 hours. This solution was poured into water and extracted with benzene. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained crystals were recrystallized from hexane-benzene to obtain the title target (1,2
6g) was obtained.

Melting point: 82.0-85.6°C Synthesis of 1-12-t-butyl-4-chloro-5-(4-trifluoroacetylbenzylthio)-3(2H)-pyridazinone (compound 70) 4'-Methyl- 2,2,2-trifluoroacetophene (2,79 g), N-promo succinimide (
2.64g) and benzoyl peroxide (0.1g) were dissolved in carbon tetrachloride (20ml) and stirred under reflux for 1 hour.

After cooling to room temperature, succinimide was filtered off.
The solvent was distilled off under reduced pressure to obtain 4-trifluoroacetylbenzyl bromide (5.09 g).

2-t-butyl-4-chloro-5-mercapto-3 (2
H)-pyridacy/7 (1,09 g) and 4-trifluoroacetylhensyl bromide (1,33 g) with N
The mixture was dissolved in N-dimethylformamide (10 ml), added with sodium carbonate (0.53 g), and stirred at room temperature for 18 hours. This solution was poured into water and extracted with benzene. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained crystals were recrystallized from hexane-benzene to obtain the title target (1.63 g ) was obtained.

Melting point: 158.0-161.0℃ 2-t-butyl-4-chloro-5-[4-(
Synthesis of 2,2,2-trifluoroethoxycarbonyl)benzylthio)-3(2)1)-pyridazinone (
Compound 144) 2-t-butyl-4-chloro-5-mercapto-3 (2
H)-pyridazinone (2,1 g) and 4-(2,2
,2-)lifluoroethoxycarbonyl)benzyl bromide (3.0 g) was dissolved in N,N-dimethylformamide (
50 nl), added sodium carbonate (1.5 g), and stirred at room temperature for 10 hours.

This solution was poured into water and extracted with benzene. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained crystals were recrystallized from hexane to obtain the title object (3.6 g).
I got it.

Melting point: 118-121''C Next, Table 3 shows production examples of compounds produced according to the methods of Production Examples 1 to 4. The compound numbers correspond to Tables 1 and 2.

Table 3 27147.1-151.0 70158-16128
159.8-167.9 143116-117338
2.0-85.6 144118-12139123.
0-124.1 217149.5-150.5401
39.8-143.1 218193-1954512
0.3-122.3 270162-163 [Hereinafter, blank space] When using the compound of the present invention as an insecticide, acaricide, nematocide for agricultural and horticultural purposes, and as a repellent for mites parasitic on animals, an appropriate compound is generally used. A carrier, such as a solid carrier such as clay, talc, bentonite, diatomaceous earth, or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons R (
benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.)
It can be applied by mixing with a liquid carrier such as acid amide (dimethylformamide, etc.), and if desired, an emulsifier,
By adding a dispersing agent, suspending agent, penetrating agent, spreading agent, stabilizer, etc., it can be put to practical use in any desired dosage form such as a liquid, emulsion, wettable powder, powder, granule, or flowable solution. In addition, other herbicides, various insecticides,
It may be applied in combination with fungicides, plant growth regulators, synergists, etc.

The amount of the compound of the present invention to be applied varies depending on the application situation, application time, application method, target pests, cultivated crops, etc., but in general, the amount of active ingredient is 0.005 to 50 per hectare.
Approximately 1 kg is appropriate.

Next, examples of formulations of insecticides, acaricides, nematicides, and agents for killing mites parasitic on animals containing the compound of the present invention as an active ingredient will be shown, but the present invention is not limited to these. In addition, in the following formulation examples, "parts" mean parts by weight.

■L Emulsion Compound of the present invention -------20 parts Xylene ---55 parts N,N-dimethylformamide ---20 parts Trupol 2680 --- --- 5 copies (
Mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industries (trade name: Mugiku) and above are mixed uniformly to form an emulsion. When using the above emulsion,
When diluted 0 times, the amount of active ingredient per hectare is o,,o
Spray to os~50kg.

Formulation Example 2 Wettable powder Compound of the present invention ----------25 parts Sieglite P F P ----------
66 parts (mixture of kaolinite and sericite; Zeeklite Industries ■trade name) Tsurupol 5039 ------- 4 parts (
Anionic surfactant: Toho Chemical Industry ■Product name) Carplex #80 -------- 3 parts (
White carbon: Shionogi &Co.'s trade name) Calcium lignin sulfonate ------- 2 or more parts are uniformly mixed and pulverized to make a wettable powder.

When using, dilute the above hydrating agent 50 to 20,000 times to obtain an active ingredient amount of 0.005 to 50k per cup.
Spread it so that it becomes g.゛Formulation Example 3 Oil Agent - 10 parts of the compound of the present invention ------- 90 parts or more of Methyl Celsolve ------- 90 parts or more are mixed uniformly to prepare an oil agent. When using the above oil agent, the amount of active ingredient is 0.005 to 50k per hectare.
Spread it so that it becomes g.

■ Powder retention agent Compound of the present invention ---3.0 parts Carplex #80 ---0.5 parts (White Carbon: Shionogi & Co. ■Product name) Clay
----------- 95 parts diisopropyl phosphate ----------- 1.5 parts or more are uniformly mixed and pulverized to form a powder. In use, the above-mentioned powder is spread so that the amount of active ingredient is 0,000 to 50 kg per hectare.

Preparation Example 1 - Granules Compound of the Invention --- 5 parts Bentonite --- 54 parts Talc --- 40 parts Calcium ligninsulfonate --- One or more parts are uniformly mixed and pulverized, a small amount of water is added, the mixture is stirred, the mixture is granulated using an extrusion type granulator, and the mixture is dried to form granules. When using the above granules, the amount of active ingredient is 0.005 to 50 per hectare.
Spread it to make a total of kg.

Planked coal L Flowable agent Compound of the present invention ------- 25 parts Tsurupol 3353 ------- 10 parts (
Nonionic surfactant: Toho Chemical Co., Ltd. (■Product name) Lunox 100OC---0.5 parts (Anionic surfactant: Toho Chemical Co., Ltd. (■Product name) 1% xanthan gum aqueous solution---- ---20 parts (natural polymer) Water ---
--44.5 parts The above components except for the active ingredient (the compound of the present invention) are uniformly dissolved, and then the compound of the present invention is added and stirred thoroughly, followed by wet grinding in a sand mill to obtain a flowable agent. When using, the above flowable agent should be added at a rate of 50 to 20
When diluted 1,000 times, the amount of active ingredient per hectare is 0.
0.005 to 50 kg.

The compound of the present invention has excellent insecticidal power against Hemiptera pests such as leafhopper, Lepidoptera pests such as diamondback moth, Coleoptera pests, and sanitary pests such as Culex mosquito, and also has excellent insecticidal power against various mites that parasitize fruit trees and sulfur vegetables, such as , two-spotted spider mite, Kanzawa spider mite, false two-spotted spider mite, citrus spider mite, apple spider mite, etc., and mites parasitic on animals such as the American spider mite,
It is also effective in controlling Boophilus annulatus, Amplionma maculatum, Libicephalus appendeiclarcus, and the staghorn tick.

It is also effective in controlling various nematodes that parasitize fruit trees and canola, such as Nematode nematode, Negusare nematode, Cyst centiellae, etc.

It is also excellent as an exterminator for mites parasitic on livestock such as cows, horses, sheep, and pigs, poultry, and animals such as dogs, cats, and rabbits.

This will be specifically explained in the following test examples.

[Margin below]

m± Insecticidal test against black leafhopper An emulsion containing the compound of the present invention was diluted with water to prepare a chemical solution with a concentration of 11,000 pp. Rice stems and leaves were immersed in this chemical solution for about 10 seconds, placed in a glass cylinder, and 10 adult leafhoppers, which are resistant to organophosphorus insecticides, were released.
A perforated plastic lid was placed on top. This cylinder is 2
The animals were housed in a constant temperature room at 5° C., and the mortality rate after 96 hours was calculated using the following formula.

The test was conducted in two sections.

As a result, the following compounds showed a mortality rate of 100%.

Compounds of the present invention No. 28, No. 39, No. 4
0, No, 45 Wipe axillary charcoal 1 Contact insecticidal test against Japanese lady beetle The emulsion containing the compound of the present invention was diluted with water and 11000
A chemical solution with a pp concentration was adjusted. Tomato leaves were immersed in this chemical solution for about 10 seconds, air-dried, and then placed in a petri dish.Into this, 10 adult 2nd instar larvae of the Japanese ladybug per petri dish were placed. accommodated in
The mortality rate after 96 hours was calculated from the following formula. The test was conducted in two sections.

As a result, the following compounds showed a mortality rate of 100%.

Compounds of the present invention No. 28, No. 39, No. 2
18M Acaricidal efficacy test against Kanzawa spider mites Green bean leaves were cut into circles with a diameter of 1.5 cm using a leaf punch and placed on moist filter paper on a styrofoam cup with a diameter of 7 cm. This was inoculated with 10 Kanzawa spider mite larvae per light. Half a day after inoculation, the emulsion containing the compound of the present invention was diluted with water to which a spreading agent was added to give 11,000p.
A drug solution with a concentration of p was adjusted. This chemical solution was sprayed at a rate of 2 mβ per styrene cup using a rotating two-spraying tower.
The mortality rate after the passage of time was calculated using the following formula. In addition,
The test was conducted in two sections.

As a result, the following compounds showed a mortality rate of 100%.

Compounds of the present invention No. 27, No. 39
Nematicidal efficacy test against Nematode nematode Contaminated soil with Nematode nematode was placed on a styrene cup with a diameter of 8 cm. An emulsion containing the compound of the present invention was diluted with water to which a spreading agent was added to prepare a 11,000 pp' (9%) chemical solution.
The soil was irrigated in an amount of 1 ml. After 48 hours, tomato seedlings of the indicator crop were transplanted. After 30 days of transplantation, the roots of the tomato plants were washed with water and inspected for Nekopu parasitism.

The test was conducted in two sections.

As a result, it was found that the following compounds exhibited strong nematicidal activity with almost no nematicidal activity observed.

Claims (2)

[Claims] (1) General formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼3(2H)-pyridazinone derivatives represented by [I]. [In the formula, R represents an alkyl group having 1 to 6 carbon atoms, and A is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
represents an alkoxy group, an alkylthio group having 1 to 4 carbon atoms, or a hydrogen atom, X represents an oxygen atom or a sulfur atom, and R^1, R^2, R^3 and R^4 each independently represent hydrogen. Represents an atom or a lower alkyl group having 1 to 4 carbon atoms, m represents 0 or 1, and Q represents ▲Mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, tables, etc.▼,▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where Y is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a carbon Alkylthio group having 1 to 4 carbon atoms or 1 to 4 carbon atoms
represents an alkylsulfonyl group, n represents 0, 1 or 2, and Z represents an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a haloalkyl group having 1 to 9 carbon atoms, or a haloalkyl group having 1 to 9 carbon atoms. There are 6 haloalkoxy groups, alkenyloxy groups with 2 to 4 carbon atoms, alkynyloxy groups with 2 to 4 carbon atoms, alkylthio groups with 1 to 4 carbon atoms, OH groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables etc. ▼ represents 0, l represents an integer from 1 to 5, R^5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R^6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. alkyl group having 1 to 4 carbon atoms, haloalkyl group having 1 to 4 carbon atoms,
Represents ~4 alkylcarbonyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ] (2) General formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼It is characterized by containing one or more 3(2H)-pyridazinone derivatives represented by [I] as an active ingredient. Agricultural and horticultural insecticides, acaricides, nematocides, and mites that are parasitic on animals. [In the formula, R represents an alkyl group having 1 to 6 carbon atoms, and A is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
represents an alkoxy group, an alkylthio group having 1 to 4 carbon atoms, or a hydrogen atom, X represents an oxygen atom or a sulfur atom, and R^1, R^2, R^3 and R^4 each independently represent hydrogen. Represents an atom or a lower alkyl group having 1 to 4 carbon atoms, m represents 0 or 1, and Q represents ▲Mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, tables, etc.▼,▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where Y is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a carbon Alkylthio group having 1 to 4 carbon atoms or 1 to 4 carbon atoms
represents an alkylsulfonyl group, n represents 0, 1 or 2, and Z represents an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a haloalkyl group having 1 to 9 carbon atoms, or a haloalkyl group having 1 to 9 carbon atoms. There are 6 haloalkoxy groups, alkenyloxy groups with 2 to 4 carbon atoms, alkynyloxy groups with 2 to 4 carbon atoms, alkylthio groups with 1 to 4 carbon atoms, OH groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, l represents an integer from 0, 1 to 5, R^5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R^6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. alkyl group having 1 to 4 carbon atoms, haloalkyl group having 1 to 4 carbon atoms,
Represents ~4 alkylcarbonyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ]