JPH0285225A - Ether compound, production thereof and use of same compound as insecticide - Google Patents

Abstract

NEW MATERIAL:An ether compound expressed by formula I (R1 is halogen or CH3; R2 is H or F; R3 is H, halogen or alkyl; R4 is lower alkyl; Y is O, S, CH2 or NH; Z is N or CH). EXAMPLE:6-phenoxy-2-pyridylmethyl 3-chloro-2,2-dimethylpropyl ether. USE:An insecticide having excellent insecticidal activity against various injurious insects of Hemiptera such as Delphacidae, Deltocephalidae, Aphididae or Pentatomidae or Diptera such as Musca domestica or Culex pipiens spallens, etc. PREPARATION:a) A compound expressed by formula II (X1 is halogen) is reacted with a compound expressed by formula III or b) a compound expressed by formula IV (A is H, methanesulfonyl or toluenesulfonyl) is reacted with halogenating agent, or c) a compound expressed by formula V (X2 is halogen) is reacted with a compound expressed by formula VI (Y' is O or S) to obtain the compound expressed by formula l.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Applicability> The present invention relates to a novel ether compound, its production method, and its use as an insecticide.

<Prior art> Until now, Japanese Patent Application Laid-Open No. 52-106881, Japanese Patent Application Laid-open No. 6
Insecticidal compounds having an ether structure are described in Publication No. 1-76462 and the like.

<Problems to be Solved by the Invention> However, it cannot be said that these compounds are necessarily fully satisfactory in their insecticidal activity.

Means for Solving the Problems In view of the above circumstances, the present inventors conducted various studies to develop a compound having excellent insecticidal activity, and as a result, the novel ether compound of the present invention has been found to be an excellent insecticidal compound. This discovery led to the present invention.

That is, the present invention relates to the general formula [wherein R1 represents a halogen atom or a methyl group,
R2 represents a hydrogen atom or a fluorine atom, R3 represents a hydrogen atom, a halogen atom or an alkyl group, and R4 represents a lower alkyl group. Y represents an oxygen atom, a sulfur atom, a methylene group or a group represented by the formula -NH-, and Z represents a nitrogen atom or a group represented by the formula -CH=. The present invention provides an ether compound represented by the following (hereinafter referred to as the compound of the present invention), a method for producing the same, an insecticide containing the same as an active ingredient, and an insecticidal method using the same.

Specific pests for which the compounds of the present invention are particularly effective include Hemiptera such as planthoppers, leafhoppers, aphids, and stink bugs, Lepidoptera such as armyworms, Diptera such as Culex mosquitoes and houseflies, and German cockroaches. Examples include Ophthalmia, other orders such as Coleoptera, Orthoptera, and Isoptera.

Next, a method for producing the compound of the present invention will be described.

(Manufacturing method A) The compound of the present invention has the general formula ([) [wherein R2, R,, Y and Z have the same meanings as above, and xl represents a halogen atom. ) Compounds represented by the general formula (llll) 艮HOCH2CCH,R, (1) ■ H8 [wherein R1 and R4 represent the same meanings as above. ] Manufactured by reacting with the compound shown below.

The reaction is usually performed using N,N-dimethylformamide (DMF)
, dimethyl sulfoxide CDMSO), 1,8-dimethyl-2-imidazolidinone and tetrahydrofuran (T)
(F), 1,4-dioxane, dimethoxyethane (DM
It is carried out in an ether type solvent such as E), a hydrocarbon solvent such as benzene, toluene, hexane, or a solvent such as water, in the presence of a base such as an alkali metal hydride, hydroxide, alkoxide, or alkyl lithium. . Reaction time is usually 1~
The reaction is carried out for 72 hours at room temperature or under heating, and if necessary, a phase transfer catalyst such as crown ether (LiWA), organic quaternary ammonium salt, phosphonium salt, or sulfonium salt may be used.

(Production method B) The general formula (
1') [In the formula, R1 represents a halogen atom, R2, R3, R
, , Y and Z have the same meanings as above. 1 The compound represented by the general formula (IV) 7N7PE0''''0°H''0050'' (IY) [wherein R2, R,, R4, Y and Z represent the same meanings as above, A represents a hydrogen atom, a methanesulfonyl group or a toluenesulfonyl group. ] It can also be produced by reacting the compound represented by these with a halogenating reagent.

The reaction usually involves sulfolane, N-methylpyrrolidone, DM
SO, hexamethylphosphoric triamide (HMPA
), diethylene glycol, triethylene glycol,
Alcohol solvents such as tetraethylene glycol; ether solvents such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether; halogenated hydrocarbon solvents such as chloroform, dichloroethane, dichloromethane, carbon tetrachloride, chlorobenzene, and bromobenzene; This is carried out in a solvent such as a hydrocarbon solvent such as toluene or xylene at room temperature or under heating, usually over a period of 1 to 72 hours.

Examples of the halogenation reagent include hydrogen halide, phosphorus halide compounds such as phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, phosphorus oxybromide, triphenylphosphine civalide, sulfur halide compounds such as thionyl chloride, Examples include alkali metal halides such as potassium chloride, cesium fluoride, and potassium iodide, and alkaline earth metal halides such as calcium fluoride.

Further, in this reaction, crown ethers can also be used if necessary.

(Production method C) General formula (1') in which Y represents an oxygen atom or a sulfur atom, Z represents a nitrogen atom, and R1 is a methyl group in the compound of the present invention [wherein, R2, R3, and R4 are as described above] and Y' represents an oxygen atom or a sulfur atom. ] The compound represented by the general formula (V) [wherein R1 and R4 represent the same meanings as above, and
, represents a halogen atom. ] and the compound represented by the general formula (Vl) Rs+ Y'H(Vl) [wherein R3 and Y' represent the same meanings as above. ] It can be produced by reacting with the compound shown below.

The reaction is usually carried out using DMF, DMSO1HMPA, toluene,
It is carried out in a hydrocarbon solvent such as xylene or without a solvent in the presence of a base such as an alkali metal hydride, hydroxide, carbonate, or alkoxide. Reaction time is usually 1-72
If necessary, a phase transfer catalyst such as crown ethers, organic quaternary ammonium salts, phosphonium salts, and sulfonylano salts, or catalysts such as copper powder or copper salts may be used.

When using the compound of the present invention as an active ingredient of an insecticide,
It may be used as is without adding any other ingredients, but
Usually, it is combined with solid carriers, liquid carriers, gaseous carriers, surfactants, other formulation auxiliaries, baits, etc., or impregnated into base materials such as incense sticks and mats to form emulsions and wettable powders. , powder,
It is used in formulations such as granules, oils, aerosols, heating fumigants such as mosquito coils and electric mosquito repellent mats, fogging agents such as fogging, non-heating fumigants, and poison baits.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.01% to 96%.

The solid carriers used include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aliphatic hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene, halogenated hydrocarbons such as dichloroethane, trichloroethylene, and carbon tetrachloride, and methanol. , alcohols such as ethanol, isopropanol, ethylene glycol, and cellosolve; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and isophorone; ethers such as diethyl ether, dioxane, and tetrahydrofuran;
Esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide,
Examples include vegetable oils such as soybean oil and cottonseed oil. Examples of the gaseous carrier include chlorofluorocarbon gas, LPG (liquefied petroleum gas), dimethyl ether, and the like.

Surfactants used in the first stage of emulsification, dispersion, wet spreading, etc. include alkyl sulfate salts, alkylaryl sulfone T31 salts, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate salts, and naphthalene sulfones. Anionic surfactants such as acid-formalin condensates, polyoxyethylene alkyl ethers,
Examples include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Formulation aids such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin,
Examples of stabilizers include CMC (carboxymethyl cellulose), pine oil, agar, etc., and examples of stabilizers include alkyl phosphates such as PAP (isopropyl acid phosphate), TCP (1) A [) ricresyl), vegetable oils, epoxidized moieties, and the above-mentioned surfactants, antioxidants such as BIT and BHA, fatty acid salts such as sodium oleate and calcium stearate, and fatty acid esters such as methyl oleate and methyl stearate.

The preparation thus obtained is used as it is or diluted with water. It can also be used in combination with other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc.

When the compound of the present invention is used as an insecticide, the applied amount is usually 51 to 500 f per 10 ares, emulsion,
When applying wettable powders etc. after diluting them with water, the application concentration is 10 ppm to 11,000 ppm, and powders, granules, oils, aerosols, etc. are applied as a preparation without diluting it in any way.

<Example 1> The present invention will be explained in more detail below using production examples, formulation examples, and test examples, but the present invention is not limited only to these examples.

First, a production example of the compound of the present invention will be shown.

Production Example 1 [Production of the present compound (1) by Production Method A] Sodium hydride (60% oily) under nitrogen atmosphere
0.65 f/ dry moth DMFIOs? suspended in
While cooling with water, a solution prepared by dissolving 8.28f of 2-chloromethyl-6-fethoxypyridine and 2.0Of of 8-chloro-2,2-dimethylpropanol in 10ml of dry DMF was added dropwise, and then kept at room temperature for 12 hours. After stirring, reaction 1
The mixture was poured into dilute hydrochloric acid-ice water and extracted twice with diethyl ether. The ether layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain the desired 6-
Phenoxy-2-pyridylmethyl 8-chloro-2,2
-dimethylpropyl ether (compound of the present invention (1)
) 0.529 was obtained as a colorless oil.

Bow'L01.5425'H-NMR data (CDC13 solvent, TMS internal standard) δ value (1) pm) 1.01 (s, 6H) 8.
135 (s, 2H) 8.5G (s, 2H) 4.52
(s, 2H) 6.62-7.82 (m, 8H) Production 12 [Production of the present compound (A) by Production Method A] 2-chloromethyl-6-phenoxy used in Production Example 1 2-chloromethyl-5-fluoro-6-funinoxypyridine 8.4 instead of pyridine 8.2af
The desired 5-fluoro-6-phenoxy-2-pyridylmethyl 3-chloro-2゜2-dimethylpropyl ether (the present compound (2B)') was prepared in the same manner as in Production Example 1 except that 9N was used. 0.719 °C was obtained as a colorless oil.

n♂'1.5880'H-NMR data (CDCd, solvent, TMS internal standard) δ value (Ppm) 1.02 (S, 6H) 8.35
(S, 2H) 8.51 (s, 2H) 4.52
(s, 2H) 6.65-7.75 (m, 7H) Production Example 8 [Production of compound (2) of the present invention by production method B] Potassium fluoride 10F was added to 100 ml of diethylene glycol, and the mixture was heated under reduced pressure (100-20 Fighting Hy) 170 below
It was heated to ~190'C and approximately 50 liters of diethylene glycol was distilled off. After cooling to room temperature, 6-phenoxy-2
-pyridylmethyl 8-methanesulfonyloxy-2,
1.27f of 2-dimethylpropyl ether was added and heated to 200°C for 8 hours. After cooling, the reaction solution was poured into ice water and extracted twice with ethyl acetate. The ethyl acetate layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography using developing solvent: hexane:ethyl acetate=
50:1), Rf value (silica gel, hexane:
A portion corresponding to 0.7 to 0.8 ethyl acetate (8:1) was collected. Furthermore, this was subjected to preparative thin layer chromatography using a developing solvent (toluene:diethyl ether = 20:1) and the desired 6-phenoxy-2-
Pyridylmethyl 8-fluoro-2゜2-dimethylpropyl ether (compound of the present invention (2) > 146 #
was obtained as an oil. (Purity 88%) n O'-'1.5809') l-NMR data (CDC1, solvent, TMS internal standard) δ value (ppm) 1.00 (b s = 6
H) 8.80 (b 8 # 2H) 4.22 (d
, 2H) 4.50 (9, 2H) 6.62-7.86 (
m, 8H) "F-NMR data (cDcn, solvent, CF3COOH
External standard (+76.51) 1) m') ) δ value (pl) m) +224.8 (bt) Production example 4 [
Production of compound (7) of the present invention by production method B] 6-phetoxy-2-pyridylmethyl 8-hydroxy-2,2-
Dimethylpropyl ether1. Of and 8.7 f of triphenylphosphine were dissolved in dry THF 15s+j, and 2.81 carbon tetrabromide was added while cooling with water, followed by stirring at room temperature for 14 hours. 45 g of hexane was added to the reaction solution to remove the formed insoluble matter, and the reactor solution was washed with water and then with saturated brine, and then concentrated under reduced pressure. Hexane was added to the residue again to remove insoluble materials, and the F solution was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (developing solvent: hexane: ethyl acetate = 50:1) to obtain the desired 6-phenoxy-2-pyridylmethyl 3-bromo-2,2-dimethylpropyl ether (the present invention). Compound (7)) 0.7
7f was obtained as a colorless oil.

n28"1.5545'H-NMR data <CDC!Is solvent, 'I'MS internal standard) δ value (ppm) 1.02 (s, 6H) 8
．． 81 (S, 2H) 8.40 (s, 2H) 4.49
(S*2H) 6.60-7.78 (m, 8 H) Production Example 5 [Production of the present compound (17) by Production Method A 145% aqueous sodium hydroxide solution 4.4 F, tetrabutylammonium bromide 1001f and 5 ml of toluene were mixed, and under a nitrogen atmosphere, a solution of 0.71 f of 2,2-dimethylbutanol and 1.72 f of 2-chloromethyl-6-funinoxypyridine dissolved in 10 g of toluene was heated to room temperature. added. After 12 hours, the reaction solution was poured into hydrochloric acid-ice water, extracted twice with diethyl ether, and the ether layers were combined and washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and the residue was subjected to preparative thin layer chromatography (developing solvent: hexane: ethyl acetate = 5:
1) to obtain 0.45f of the desired 6-phenoxy-2-pyridylmethyl 2,2-dimethylbutyl ether (the compound of the present invention (17)) as an oil.

Heart 1°'1.5250'H-NMR data (CDC13 solvent, TMS internal standard) δ value (PI) m) 0.82 (bt, 8H) 0.
92 (s, 6H) 1.20-1.55 (m, 2H) 8.24 (8, 2H) 4.51 (s, 2H) 6.65
(bd, IH) 7.00-7.80 (m.

7H) Production Example 6 [Production of compound (1) of the present invention by production method B] 0.5 f of 6-funinoxy 2-pyridylmethyl 8-hydroxy-2,2-dimethylpropyl ether was dissolved in 20 g of dry xylene, 0.78 f of phosphorus pentachloride was added and the mixture was heated under reflux for 8 hours. Next, pour the reaction solution into ice water,
Extracted with xylene. The xylene layer was washed with water, dried and concentrated, and the resulting residue was subjected to silica gel column chromatography (developing solvent: hexane: ethyl acetate = 50:1) to obtain the desired 6-phenoxy-2-pyridylmethyl 8-chloro- 90 capes of 2,2-dimethylpropyl ether (the compound (1) of the present invention) were obtained.

'H-NMR data (CDC1, solvent, TMS internal standard) δ value (ppm) 1.00 (s, 6H) 8.8
2 (s, 2H) 8.48 (8, 2H) 4°51 (8
, 2H) 6.60-7.80 (m, 8H) Production Example 7 [Production of the present compound (8) by Production Method A] 2-chloromethyl-6-phenoxypyridine used in Production Example 1 8.28f The desired 4-fluoro-8-phenoxybenzyl 8-chloro-2,2-dimethyl was obtained by the same procedure as in Production Example 1 except that 4-fluoro-8-phenoxybenzyl bromide 4.18F was used instead. 8.79 f of propyl ether (inventive compound (3)) was obtained as a colorless oil.

n, 1.5401 'H-NMR data (CDC6, solvent, TMS internal standard) δ value (ppm) 1.01 (s, 6H) 8.8
5 (s, 2H) 8.51 (S, 2H) 4.40 (8
, 2H) 6.80-7.45 (m, 8H)"F-
NMR data (CDCAs solvent, CF, C0OH external standard (+ 76.5 ppm)) δ value (ppm) + 129.8 (m) Production example 8
[Production of compound (17) of the present invention by production method C] 1.86 f of phenol was dissolved in lOs+l of xylene, and 0.74 f of sodium hydroxide was added.

The reaction solution was heated under reflux for 6 hours while removing by-product water using a column filled with calcium chloride. 6-chloro-
2-Pyridylmethyl 2,2-dimethylbutyl ether B,Of and cuprous chloride 800F were added and the mixture was further heated under reflux for 8 hours. After cooling, the reaction solution was poured into dilute hydrochloric acid and ice water.
Extracted with xylene. After washing the xylene layer with water and drying, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: hexane: ethyl acetate = 50:1).
) to obtain 8.41 pieces of the desired 6-phenoxy-2=pyridylmethyl 2,2-dimethylbutyl ether (the compound of the present invention (17)) as an oil.

'H-NMR data (CDCl8, TMS internal standard) δ
Value (pl) m) 0.80 (bt, 8H) 0.9
1(S, 6H) 1.19-1.54Un, 214) 8
．． 22 (s.

2) 1) 4.50 (s, 2H) 6.55~? , 80 (m, 8H) Production Example 9 [Production of the present compound (35) by production method A] 45% sodium hydroxide water H16s in a nitrogen atmosphere,
8ay, mix 120q of tetrabutylammonium bromide and 5 ml of toluene, and add 2-ethyl-2-methylbutanol t,oy and 1.51F of 6-phenoxy-2-chloromethylpyridine to 5 ml of toluene to the mixed solution. The dissolved solution was added at room temperature.

After continuing to stir at room temperature for 16 hours, the reaction solution was poured into dilute hydrochloric acid-ice water and extracted twice with toluene. The toluene layers were combined, washed with saturated saline, dried over anhydrous magnesium sulfate,
The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: hexane: ethyl acetate = 50:1) to obtain the desired 6-phenoxy-2-
Pyridylmethyl 2-ethyl-2-methylbutyl ether (the present compound (85)) 1.48F was obtained as a colorless oil.

nD”L, 5270 H-NMR data (CDC13 solvent, TMS internal standard)
δ value (ppm) 0.68 to 1.00 (m, 9H) 1
．． 15-1.60 (m, 4H) 8.28 (s.

2H) 4.51 (・8, 2H) 6.60-7.78
(m, 8H) Production Example 10 [Production of Compound (35) of the Present Invention by Production Method C] 0.761 ml of phenol was dissolved in 5 ml of xylene, and 0.8 F of sodium hydroxide was added thereto.

The reaction solution was heated under reflux for 4 hours while removing by-product water using a column filled with molecular sieves 4A. Cool to room temperature and add 6-chloro-2-pyridylmethyl 2-
A solution of ethyl-2-methylbutyl ether t, aoy dissolved in 6 ml of xylene and cuprous chloride 1 B 01
g was added thereto, and heating and refluxing was continued for 8 hours. After cooling, the reaction solution was poured into dilute hydrochloric acid-ice water and extracted with xylene. After washing the xylene layer with water and drying, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent;
Hexane:ethyl acetate=50:1) Desired 6-phenoxy-2-pyridylmethyl 2-ethyl-2-methylbutyl ether (compound of the present invention (85)) 1.22
F was obtained as a colorless oil.

2 tons On 1.5272'H-N*R data (CDC13 solvent, TMS internal standard) δ value (ppm) 0.69~t, o2 (m,
9 H) 8.29 (8,2H) 4.51 (8,2H) Some of the compounds prepared in the same manner as above are shown in Table 1.

Examples of formulations are shown below. The compounds of the present invention are indicated by the compound numbers listed in Table 1. Parts are parts by weight.

Formulation Example 1 0.2 parts of each of the compounds (1) to (47) of the present invention, 2 parts of xylene, and 97.8 parts of white kerosene are mixed to obtain an oil solution.

Formulation Example 2 10 parts each of the compounds (1) to (47) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene are thoroughly mixed to obtain an emulsion.

Formulation Example 8 Compounds of the present invention (1), (3), (18), (17), (
20 parts each of 88) or (85), 10 parts of phenitrothion, 8 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 4 Compounds of the present invention (1), (2), (6), (8), (10
), (34) or (36), 2 parts of carbaryl, 87 parts of kaolin clay and 10 parts of talc (
Grind and mix to obtain a powder.

Formulation Example 6 6 parts each of the compounds of the present invention (1), (2), (17), (88) or (87), 1 part of synthetic hydrated silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and kaolin clay. After thoroughly pulverizing and mixing 62 parts, adding water and kneading well, the mixture is granulated and dried to obtain granules.

Formulation Example 6 Compounds of the present invention (1), (3), (6), (13), (8
0.05 parts each of 4) or (88), 0.2 parts of tetramethrin, 0.05 parts of Res 1920, xylene 7i, Ba
! After mixing and dissolving 82.7 parts of kerosene, filling it into an aerosol container and attaching a valve part, 60 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol.

Formulation Example 7 Each of the compounds (1), (6), or (47) of the present invention is 0.
81 and allethrin d-trans primary chrysanthemum acid ester 0.
Add 8y, dissolve in 20 ml of methanol, stir and mix uniformly with 99.4F carrier for mosquito coils (mixing tab flour: lees flour: wood flour in the ratio of 8:5:l), and evaporate the methanol. After that, add 150 ml of water, mix well, mold and dry to obtain each mosquito coil.

Next, test examples did not demonstrate that the compounds of the present invention are useful as active ingredients of insecticides. The compounds of the present invention are indicated by the compound numbers listed in Table 1, and the compounds used as comparison controls are indicated by the compound numbers listed in Table 1.
Tube listed in table 2 Table Test Example 1 Place P paper of the same size on the bottom of a polyethylene cup with a diameter of 5.51 mm. 0.7 ml of a 200-fold dilution with water of an emulsion of the compound of the present invention prepared according to Formulation Example 2 (active ingredient concentration 500 ppm) was dropped onto P paper, and 80 da of sucrose was added uniformly as bait. . Ten female adult house flies were released into the container, the lid was closed, and 24 hours later, their survival was examined (2
repetition).

The results are shown in Table 1g8.

Table 8 Test Example 2 Rice stalks (length about 121 cm) were added to 1 m) of a 6670-fold dilution of the emulsion of the present invention compound and control compound below obtained in Formulation Example 2 with water (active ingredient concentration 15 m). Soaked for minutes. After air-drying, rice stems were placed in a tester and 10 adult leafhoppers of the resistant strain were released, and one day later, the survival and death were examined to determine the mortality rate (2 repetitions).

The results are shown in Table 4.

Table 4 Test Example 8 Rice stems (length approximately 121 cm) were immersed for 1 minute in a 6670-fold dilution in water of an emulsion of the following inventive compound and control compound obtained according to Formulation Example 2 (active ingredient concentration 15 ppm). did. After air-drying, the rice stems were placed in a test tube and 10 adult black kites and brown planthoppers were released, and one day later, they were examined to see if they were alive or dead, and the mortality rate was determined (2 repetitions).

The results are shown in Table 6.

Table 5 Test Example 4 A 1000-fold dilution in water of an emulsion of the following inventive compound and control compound obtained according to Formulation Example 2 (active ingredient concentration 100 ppm) was added to rice seedlings planted in polyethylene cups in an amount of 20 g+// Sprayed at a rate of 2 pots. After air-drying, the pot was covered with a wire mesh, and approximately 15 adult I. metobii planthoppers were released in each pot, and the mortality rate was determined by examining whether they were alive or dead after 1 day (2 repetitions).

The results are shown in Table 6.

Table 6 <Effects of the Invention> The compounds of the present invention exhibit excellent insecticidal efficacy against various pests such as Hemiptera such as planthoppers, leafhoppers, aphids, and stink bugs, and Diptera such as houseflies and Culex mosquitoes. Because of this, it can be used for various purposes.

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Claims (6)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 represents a halogen atom or a methyl group, R_2 represents a hydrogen atom or a fluorine atom, and R_3
represents a hydrogen atom, a halogen atom or an alkyl group,
R_4 represents a lower alkyl group. Y represents an oxygen atom, a sulfur atom, a methylene group or a group represented by the formula -NH-, and Z
represents a nitrogen atom or a group represented by the formula -CH=. ] An ether compound represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_2 represents a hydrogen atom or a fluorine atom,
R_3 represents a hydrogen atom, a halogen atom, or an alkyl group. X_1 represents a halogen atom, Y is an oxygen atom,
It represents a sulfur atom, a methylene group or a group represented by the formula -NH-, and Z represents a nitrogen atom or a group represented by the formula -CH=. ] Compounds and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents a halogen atom or a methyl group, and R_4 represents a lower alkyl group. 2. The method for producing an ether compound according to claim 1, wherein the ether compound is reacted with a compound represented by: (3) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_2 represents a hydrogen atom or a fluorine atom,
R_3 represents a hydrogen atom, a halogen atom, or an alkyl group, and R_4 represents a lower alkyl group. Y represents an oxygen atom, a sulfur atom, a methylene group or a group represented by the formula -NH-, Z represents a nitrogen atom or a group represented by the formula -CH=, and A represents a hydrogen atom, a methanesulfonyl group or a toluenesulfonyl group represents. ] A general formula characterized by reacting the compound represented by the above with a halogenating reagent ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R'_1 represents a halogen atom, R_2, R
_3, R_4, Y and Z have the same meanings as above. ] A method for producing an ether compound shown by. (4) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_2 represents a hydrogen atom or a fluorine atom,
R_4 represents a lower alkyl group. X_2 represents a halogen atom. ] Compounds and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_3 represents a hydrogen atom, a halogen atom, or an alkyl group. Y' represents an oxygen atom or a sulfur atom. [In the formula, R_2, R_3, R_4 and Y' have the same meanings as mentioned above. ] A method for producing an ether compound shown by. (5) An insecticide containing the ether compound according to claim 1 as an active ingredient. (6) An insecticidal method using the ether compound according to claim 1.