JPS63215674A - Pyridazinone derivative and controlling agent against insect pest - Google Patents

Abstract

NEW MATERIAL:A 3(2H)-pyridazinone derivative expressed by formula I (R is 1-6C straight-chain or branched alkyl; A is H, halogen, 1-4C alkoxy or 1-4C alkylthio; X is O or S; R<1> and R<2> are H, 1-4C alkyl or halogen; R<3> is 1-4C haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfonyl, alkoxycarbonyl, alkylcarbonyl, 2-4C alkenyl, alkynyl, halogen or cyano; B is aryl). EXAMPLE:4-Chloro-2-tert-butyl-5-[ 1-( 4-tert-butylphenyl )-2, 2, 2-trifluoroethoxy ]-3 (2H)-pyridazinone. USE:An agricultural and horticultural insecticide, acaricide, nematocide and expel lent against mites parasitic on animals. PREPARATION:Compounds expressed by formulas II and III [X' and X'' are halogen atom, -SM or -OM (M is H or alkali metal atom)] are reacted to afford the aimed compound expressed by formula I.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides novel 3 (2H)-pyridazinone derivatives,
The present invention relates to a method for producing the same, and an insecticide for agricultural and horticultural use, an acaricide, a nematocide, and a repellent for mites parasitic on animals, which contain the derivative as an active ingredient.

[Conventional technology]

The following patents are related to the present invention: European Patent Publication No. 0088384 European Patent Publication No. 0134439 European Patent Publication Older European Patent Publication No. 83212 European Patent Publication No. 0199281 European Patent Publication No. 0210647 The known compounds contained in these patents are generally Formula (n)
It is expressed as

The characteristics of these patents are 1. For example, European Patent Publication 00
In No. 88384 and European Patent Publication No. 0134439, -Y' is an oxygen atom or a sulfur atom.

-8'-Q' is a benzyl group derivative directly substituted with an alkyl group at the α position, and in European Patent Publication No. 0183212, A'' is an alkyl group or B'' is a double bond, In European Patent Publication No. 0199281, Q'' is a heterocycle or has a special substituent introduced, and in European Patent Publication No. 0210647, R'' is an aryl group. It is where it is.

In this way, the chemical structure is also different from that of the present invention.

C Embodiment of the Invention] Since then, the present inventors have continued to conduct intensive research on pyridazinone derivatives. As a result, the compound represented by the general formula [■] :H'' was reacted with the compound represented by the general formula [■] : to obtain the compound of the present invention represented by the general formula (1).

[In the formula, R represents a linear or branched alkyl group having 1 to 6 carbon atoms, A is a hydrogen atom,) hrogen atom, C
1-C4 alkoxy group or 01-C4 alkylthio group, X represents an oxygen atom or a sulfur atom, R1 and RZ each independently represent a hydrogen atom, a C1-C4 alkyl group or a /'t rogen atom, R3 is Carbon number 1~
4/'t loalkyl group, alkoxy group, haloalkoxy group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group or alkylcarbonyl group, or an alkenyl group or alkynyl group having 2 to 4 carbon atoms, or a halogen atom, a cyano group, represents an aryl group or an arylmethylene group, B represents an aryl group, Xo and X I + represent a halogen atom, - or 10M (M represents a hydrogen atom or an alkali metal atom). However, when X I is a halogen atom, X l 1 represents -5M or 10M, and Xo is -
In the case of SM or one leaf, X°'' represents a halogen atom.

Z is a halogen atom and a 3-alkylcarbonyloxy group.

Represents an alkylsulfonyloxy group or an arylsulfonyloxy group. Furthermore, the present inventors have discovered that the compound of the present invention represented by the general formula (1) has excellent insecticidal, acaricidal, and nematicidal effects.

For example, the known compounds represented by the general formula (n) had strong insecticidal, acaricidal, and nematocidal activities, but the compounds of the present invention have stronger insecticidal, acaricidal, and nematocidal activities. showed a significant increase in activity. Therefore, compared to the known compound group represented by the general formula (11), the compound of the present invention has
We have completed the present invention by discovering that insects harmful to agriculture and horticulture can be effectively controlled with extremely low chemical concentrations.

In the above general formula (1), H3 is an aryl group or the aryl group in the arylmethylene group and the aryl group of B mean an unsubstituted or substituted phenyl group. Types of substituents include 1, for example, halogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkyloxy group, 7 alkenyloxy group, alkynyloxy group, alkylthio group, alkenylthio group, alkylsulfinyl group, alkylsulfonyl group. Base.

cycloalkyloxy group, haloalkyl group, haloalkyloxy group, haloalkylthio group, alkylamino group,
Alkylcarbonylamino group, nitro group, cyano dihydroxyl group, alkylcarbonyl group.

Alkoxycarbonyl group, carboxyl group, aryl group, aryloxy group, arylthio group, arylamino group, arylcarbonyl group, arylmethyleneoxy group, aryloxymethyl group.

Arylmethylenecarbonyl group, unsubstituted or substituted pyridyloxy group, hydroxyalkyl group, alkylcarbonyloxyalkyl group.

Alkoxyalkyl group, alkylthioalkyl group.

Examples include an alkylcarbonylalkyl group, an alkoxycarbonylalkyl group, a cyanoalkyl group, and a haloalkylcarbonyl group.

Compounds included in the present invention include, for example, the compounds shown in Table 1. However, the compounds in Table 1 are for illustrative purposes only.

The present invention is not limited to these.

[However, in Table 1, L stands for tertiary, i stands for iso, C
stands for cyclo, S stands for secondary, Me stands for methyl group, Et stands for ethyl group, and Pr stands for propyl group.

Bu is a butyl group, Al11 is an amyl group, Pen
represents a pentyl group, Hex represents a hexyl group, and Ph represents a phenyl group. ] Among the compounds included in the present invention, in the case of a compound having an asymmetric carbon atom, the optically active (+) or (-) isomer is also included.

[Margin below]

Table 1 No. RA X R' R” R3YN
o, RA
R3YNo, RA X R'
R” R’YNo,
RA
YNo, RA X R'
R”R”YNo,
RA
3YNo, RA X R' R”
R3YNo, RA
R'R"R" YNo
, RA
R'YNo, RA
R'R"R' YNo
, RA
Ql-Q3 in R'Y Table 1 represents the following structural formula.

The compound numbers in Table 1 above are referred to in the following production examples, formulation examples, and test examples.

The compound of the present invention can be produced by reacting a compound represented by the general formula [■]: N' with a compound represented by the general formula [■]:.

Generally, when X'' in general formula (I[I) is a halogen atom, one needle or 10M is used for Xl in general formula (IV), and conversely, X'' in general formula [I[1] is used. When is -SM or -OM, a halogen atom may be used as X + + in general formula (TV).

Further, it is preferable to carry out the reaction in the presence of a suitable base in a solvent that does not affect the reaction. However, when 1M is an alkali metal atom, the presence of a base is not necessarily required.

In addition, two compounds of the present invention are obtained by reacting a compound represented by the general formula [■] : with a compound represented by the general formula [■] : R3-Z (VI) : in the presence of a base in a solvent that does not affect the reaction. It can also be manufactured by

In the present invention, the solvents include lower alcohols (eg, methanol, ethanol, etc.) and ketones (eg, 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, hexamethylphosphoric triamide, etc.), halogenated hydrocarbons (e.g., N,N-dimethylformamide, hexamethylphosphoric triamide, etc.)
For example, dichloromethane, dichloroethane, etc.) can be used. Moreover, a mixed solvent of these solvents or a mixed solvent with water can also be used as required.

Bases include inorganic bases (e.g. sodium hydride,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Potassium carbonate, sodium bicarbonate, etc.) and organic bases (eg, sodium methoxide, sodium ethoxide, triethylamine, pyridine, etc.) can be used. Moreover, a tetraammonium salt (eg, triethylbenzylammonium chloride, etc.) may be added as a catalyst to the two reaction systems, if necessary. The reaction temperature can be in the range from -20°C to the boiling point of the solvent used in the two reactions, but is more preferably in the range from -5°C 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 a ratio of 9 equimolar or close to it.

Next, the method for producing the compound of the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these.

M3iJi 4-chloro-2-t-butyl-5-(1-
Production of (4-t-butylphenyl)-2,2,2-trifluoroethoxy]-3(2H)-pyridazinone (synthesis of compound 22 of the present invention) 3.6 g of sodium borohydride was added to 160 ml of ethanol.
1, 22 g of 4'-mo-butyl-2,2,2-trifluoroacetophenone was added dropwise under water cooling, and the mixture was further stirred at room temperature for 1 hour. Acidify with acetic acid.

The residue obtained by distilling off the solvent under reduced pressure was extracted with ether, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 21.7 g of 1-(4-t-butylphenyl). )
-2,2,2-trifluoroethanol was obtained.

1.16 g of 1-(4-t-butylphenyl)-2,2,2-trifluoroethanol and 2-t-butyl-
4,5-dichloro-3(2H)-pyridazinone 1.11
g was dissolved in 10 ml of N,N-dimethylformamide, 0.42 g of potassium hydroxide was added, and the mixture was stirred at room temperature for 18 hours. This solution was poured into ice water, extracted with benzene, washed with water, and dried over anhydrous sodium sulfate.

The solvent was distilled off under reduced pressure. The obtained oil was separated and purified by column chromatography (silica gel; benzene) to obtain 1.37 g of white crystals.

Melting point: 156.9-157.6°C Kekashitan I Production of 4-chloro-5-(α-ethoxycarbonylbenzyloxy)-2-ethyl-3(2H)-pyridazinone (synthesis of the present compound No. 561) 4-chloro-2-ethyl-5-hydroxy-3(2H)
- 1.5 g of pyridazinone and 2.2 g of α-promorph, enyl acetate ethyl ester; 1.7 g of anhydrous potassium carbonate dissolved in 10 mf of methylformamide
was added and stirred at 90-100°C for 3 hours. After cooling the reaction mixture to room temperature.

The mixture was poured into 100ml of water and extracted with ethyl acetate. Wash with water.

After drying, the solvent was distilled off under reduced pressure to obtain a crude product.

This was purified by column chromatography (silica gel; benzene/ethyl acetate = 15/1) to obtain the target compound 1.
．． 8g was obtained. Oil 'H-NMR (CDCh, δ value); 1.29 (3H, t), 1.35 (311, t), 4.
19 (4H, q) 5.88 (IH, s), 7.1~7
．． 7 (5H, m), 8.95 (18, s) Charcoal owner
2-t-butyl-4-chloro-5-[bis-(4-t-
butylphenyl)-methylthio)-3(2H)-pyridazinone (synthesis of the present compound 11h63B) 2-t-butyl-4-chloro-5-mercapto-3(2
H)-pyridazinone 1.29 g, bis-(4-
1.57 g of t-butylphenyl)-chloromethane and 0.43 g of potassium carbonate were suspended in 10 ml of acetone and stirred at room temperature for 3 hours. This solution was poured into water, extracted with benzene, and washed with water. The benzene layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting oil was separated and purified by column chromatography (silica gel; benzene) to obtain 1.3 g of white crystals.

Melting point: 76.0 to 78.0°C The physical properties of the compounds produced according to any of the methods shown in Production Examples 1 to 3 are shown in Table 2 below.

Table 2 No. Melting point (°C) No. Melting point (°C
)22156.9-157.6 637100.4-1
03.0561 Oil 638 7
6.0-78.0562 Glassy substance book 1640
Oily substance *3628 Glassy substance *2 -
□NMR (CDCh, δ value): *1: 1.20 (3H, t), 1.61 (9H, s)
, 4.18(2H,q).

5.80 (III, s), 7.1-8.7 (6H, m)
*2: 1.30 (9H, s), 1.33 (3H, t)
, 4.16 (2tl, q).

6.03 (ill, s), 7.3~7.6 (
10)1. m) Umbrella 3: 1.52 (98,s), 2
．． 25 (3H, s), 3.18 (2H, d).

4.65 (IH, t), 6.9~7.4 (IOH
, m) When using the compound of the present invention as an agricultural and horticultural insecticide, acaricide, nematocide, and a mite repellent parasitic on animals, a suitable carrier 1 such as clay, talc,
Solid carriers such as bentonan diatoms or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (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 amides (dimethylformamide, etc.), and if desired, an emulsifier, a dispersant, a suspending agent, a penetrating agent, a spreading agent, a stabilizer, etc. are added.
Liquids, emulsions, wettable powders, powders.

It can be put to practical use in any dosage form such as granules or flowables. Further, if necessary, other herbicides, various insecticides, fungicides, plant growth regulators, synergists, etc. may be mixed and applied during formulation or spraying.

The amount of the compound of the present invention to be applied depends on the application situation and application period.

Although there are differences depending on the application method, target pests, cultivated crops, etc., the amount of active ingredient is generally 0.005 per hectare.
~50 kg is appropriate.

Next, insecticides and acaricides containing the compound of the present invention as an active ingredient.

Examples of formulations of nematicides and agents for killing mites parasitic on animals are shown, but the present invention is not limited thereto. In addition, in the following formulation examples, "parts" mean parts by weight.

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 Industry ■Product name) The above is mixed uniformly to form an emulsion. When used, the above emulsion is diluted 50 to 20,000 times and sprayed at an amount of active ingredient of 0.005 to 50 kg per hectare.

Seikoku Tanji Hydrating agent 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 01 product name) Carplex #! 30 ---------- 3 parts (white carbon: Shionogi & Co., Ltd. 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 50 k per hectare.
Spread it so that it becomes g.

ul Oil agent Compound of the present invention -------10 parts Methyl cellosolve --- 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.

■ Dust-retaining agent Compound of the present invention ------3.0 parts Carplex #80 ---0.5
parts (white carbon: Shionogi & Co., Ltd. am brand name) clay --- 95 parts diisopropyl phosphate --- 1.5 parts or more are uniformly mixed and pulverized to form a powder. When used, the above-mentioned powder is spread at an amount of active ingredient of 0.005 to 50 kg per hectare.

■L Granule Compound of the present invention -------5 parts Bentonite -111 to ---54 parts Talc---40 parts Calcium ligninsulfonate---1 part or more The mixture is mixed and pulverized uniformly, mixed with a small amount of water, and then granulated using an extrusion granulator and dried to form granules. When using the above granules, the amount of active ingredient is 0.005-50k per hectare.
Spread it so that it becomes g.

Embarrassing story of rupture - Flowable agent Compound of the present invention ------- 25 parts Tsurupol 3353 ------- 10 parts (
Nonionic surfactant: Toho Chemical Industries US trade name) Lunox 1000 C---0.5 parts (Anionic surfactant: Toho Chemical Industries OS trade 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, add 50 to 200
The amount of active ingredient is 0.0 per hectare when diluted 0.0 times.
Spread it so that it weighs 0.5 to 50 kg.

The compounds of the present invention have excellent insecticidal power against Hemiptera pests such as leafhoppers, Lepidoptera pests such as the diamondback moth, Coleoptera pests, and sanitary pests such as Culex mosquito, as well as various mites that parasitize fruit trees and sulfur vegetables.

For example, it is effective for controlling two-spotted spider mites, Kanzawa spider mites, false red spider mites, citrus spider mites, apple spider mites, etc., and mites parasitic on animals, such as the American spider mite, Boophilus annullitus, Amplionma macricum, Libicephalus avendiculatus, and the two-legged spider mite.

It is also effective in controlling various nematodes that parasitize fruit trees and vegetables, such as nematode nematode, nematode nematode, and cyst nematode.

This will be specifically explained in the following test examples.

A 20x emulsion of the compound of the present invention (a 25x wettable powder is used depending on the compound) described in the insecticidal test specification against leafhoppers was diluted with water containing a spreading agent to make a chemical solution with a concentration of 11,000 pp. It was adjusted. A sufficient amount of this chemical solution was sprayed on the stems and leaves of rice planted in a 1/20,000 are pot, and after air-drying, 20 second-instar larvae of the black leafhopper, which is resistant to organophosphorus insecticides and carbamate insecticides, were released per pot. The adult insects and the rice plants were covered with a cylindrical gauge made of wire mesh and stored in a constant temperature room. The investigation was conducted after 96 hours had elapsed, and the mortality rate was calculated using the following formula.

The test was conducted in two sections.

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

Compound No. 640 of Invention Group I A 20χ emulsion of the compound of the present invention (a 25χ wettable powder was used depending on the compound) described in the specifications for the insecticidal test against the Japanese lady beetle was mixed with water containing a spreading agent. The solution was diluted to a concentration of 11,000 pp, and tomato leaves were immersed in this solution for about 10 seconds, air-dried, and then placed in a petri dish, in which 10 adult second instar nymphs of Ladybug larvae per petri dish were placed.

The cells were placed in a thermostatic chamber at 25° C. with a lid with holes, 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 100% mortality rate.

Compound No. 640 of the present invention 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 styrene cup with a diameter of 7 cm. This was inoculated with 10 Kanzawa spider mite larvae per leaf. Half a day after inoculation, a 20x emulsion of the compound of the present invention described in the specification (a 25x wettable powder is used depending on the compound) was diluted with water containing a spreading agent to give 11,000 g.
pp? The chemical solution was adjusted to a degree of A degree, and this chemical solution was sprayed at a rate of 2 mff per styrene cup using a rotary scattering tower.
The mortality rate after 6 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%.

Compound No. 22 of the present invention. No.562. No. 6
37. No, 638°No, 640

Claims (2)

[Claims] (1) General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [I] [In the formula, R represents a linear or branched alkyl group having 1 to 6 carbon atoms, and A represents a hydrogen atom or a halogen atom. atom, C1
~ Represents a C4 alkoxy group or a C1-C4 alkylthio group, X represents an oxygen atom or a sulfur atom, R^1 and R^2 each independently represent a hydrogen atom, a C1-C4 alkyl group, or a halogen atom, R ^3 is carbon number 1~
4 haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group or alkylcarbonyl group, or an alkenyl group or alkynyl group having 2 to 4 carbon atoms, or a halogen atom, a cyano group, an aryl group, or It represents an arylmethylene group, and B represents an aryl group. ] 3(2H)-pyridazinone derivative represented by these. (2) General formula [I]: ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R represents a linear or branched alkyl group having 1 to 6 carbon atoms, A is a hydrogen atom, Halogen atom, C1
~ Represents a C4 alkoxy group or a C1-C4 alkylthio group, X represents an oxygen atom or a sulfur atom, R^1 and R^2 each independently represent a hydrogen atom, a C1-C4 alkyl group, or a halogen atom, R ^3 is carbon number 1~
4 haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group or alkylcarbonyl group, or an alkenyl group or alkynyl group having 2 to 4 carbon atoms, or a halogen atom, a cyano group, an aryl group, or It represents an arylmethylene group, and B represents an aryl group. ] A repellent for agricultural and horticultural insecticides, acaricides, nematicides, and mites parasitic on animals, which contains one or more 3(2H)-pyridazinone derivatives represented by the following as an active ingredient.