JPS61293944A - Ether compound, production thereof and insecticide and acaricide containing said compound as active constituent - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X is O or NH; Z is N or CH when X is O, and CH when X is NH; R1 is H or F, provided that R1 is only F when X is O and Z is CH; Y1 and Y2 are H, halogen, alkyl, haloalkyl, alkoxy or haloalkoxy; m and n are integers 1-4 when the sum is <=5; R2 is methyl or Cl; R3 is methyl, halogen or methoxy]. EXAMPLE:6-Phenoxy-2-pyridylmethyl neopentyl ether. USE:An insecticide and acaricide. PREPARATION:For example, a compound expressed by formula II (A is halogen) is reacted with an alcoholic compound expressed by formula III (R4 is methyl or Cl) in the presence of a base to affored the aimed compound expressed by formula I (X is O; R2 and R3 are R4).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel ether compound represented by the following general formula (1), a method for producing the same, and an insecticide or acaricide containing the same as an active ingredient.

[Wherein, X represents an oxygen atom or a group represented by the formula -NH-, when X represents an oxygen atom, 2 represents a nitrogen atom or a group represented by the formula -CH=, and X represents a group represented by the formula -Nu- When representing a group represented by the formula, 2 represents a group represented by the formula -CH=. When X represents an oxygen atom and 2 represents a nitrogen atom, and when X represents a group represented by the formula -NIli-, 1 represents a hydrogen atom or a fluorine atom, and
When represents an oxygen atom and 2 represents a group represented by the formula -CH=, then! represents a fluorine atom.

Yt and Yl are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, or a haloalkoxyl group, and m and n each represent an integer of 1 to 4 whose sum is 5 or less.

R2 represents a methyl group or a chlorine atom, and R3 represents a methyl group, a halogen atom or a methoxy group. ] As a result of repeated research for the purpose of developing a compound having excellent insecticidal activity, the present inventors have found that the compound of the present invention represented by the general formula (1) has: 1. High insecticidal efficacy; 2. An organic phosphorus agent or It was discovered that it has the following characteristics, and has led to the present invention: It is highly effective even against pests resistant to carbamate agents.

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 the common insect and armyworm, Diptera such as Culex mosquitoes and houseflies, and German cockroaches. Examples of the order Ophida, other orders such as Coleoptera, orthoptera, and spider mites include the red-spotted spider mite and the orange spider mite.

The compound of the present invention can be produced, for example, by the following method.

(Manufacturing corporation) General formula (I[I) [In the formula, Z, R1, Yl, Yz, m and n have the same meanings as above, and m represents a halogen atom. ] A compound represented by the following general formula (■) 54 [In the formula, R4 represents a methyl group or a chlorine atom. [In the formula, Z, R1, Yl, Y2, m, n and R4]
has the same meaning as above. ] A method for producing an ether compound shown by.

More specifically, examples of the alcohol compound represented by the general formula (IV) include aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide, tetrahydrofuran, etc. , ethers such as 4-dioxane and ethylene glycol dimethyl ether, ketones such as acetone and methyl ethyl ketone, or aromatic hydrocarbons such as benzene and toluene. It can be produced by reacting an alkali metal salt with lithium, an alkali carbonate, an alkali hydroxide, etc., and reacting the compound represented by the general formula (Ill) with the alkali metal salt under heating from 06C for 1 hour to 72 hours.

(Manufacturing method B) General formula ff) [In the formula, Z, Rr, Yl, Y2, m and n have the same meanings as above. ] A compound represented by the general formula (Vl) [wherein Y represents a halogen atom, a tosyloxy group or a mesyloxy group. ] In the general formula 0, Z, Rs, Yl, Y2, m and n have the same meanings as above. ] A method for producing an ether compound shown by.

More specifically, the compound represented by the general formula (v) may be added to an aprotic polar solvent such as dimethylformamide or dimethyl sulfoxide, or tetrahydrofuran,
(2) In organic solvents such as ethers such as 4-dioxane and ethylene glycol dimethyl ether, a base (e.g., alkali metal hydride, alkali alcoholade, alkyl lithium, etc.) is reacted to form an alkali metal salt, and the general formula (VI ) is heated from room temperature to 1 to 4.
It can be produced by reacting for 8 hours.

(Production method C) General formula (■) In the formula 0, X, Z, R1, Yl, Y2, m and n have the same meanings as above.

Compounds represented by the general formula (■) HR5 (■) [wherein Rs represents a chlorine atom, a bromine atom, or a methoxy group. ] by reacting with a compound represented by the following general formula [wherein, X, Z, R1, Yl, Y2, m, n and R5 have the same meanings as above. ] A method for producing an ether compound shown by.

More specifically, the compound represented by the above general formula (■) and the general formula (IX) HRy (■) [wherein, Ry represents a chlorine atom or a bromine atom]. ] For example, alcohols such as methanol and ethanol, halogenated hydrocarbons such as carbon tetrachloride and chloroform, fatty acids such as acetic acid and propionic acid, or aromatic hydrocarbons such as benzene and toluene. The above-mentioned ether compound in which the substituted Go stone is a chlorine atom or a bromine atom can be produced by reacting for 1 to 12 hours at 0° C. to room temperature in an organic solvent such as the following.

In addition, the compound represented by the general formula (■) was prepared in methanol in the presence of mercuric acetate at -1θ°C to room temperature for 1 hour to
After processing for 12 hours, further.

The above-mentioned ether in which the substituent R2 is a methoxy group is obtained by reacting an alkali hydroxide on the above at room temperature for 1 hour to 24 hours, and reacting the resulting product with an alkali metal borohydride at a temperature of 0°C to room temperature. compounds can be manufactured.

In the above (manufacturing method C), the compound represented by the general formula (■) can be manufactured, for example, by the route shown below.

Hs [wherein Z, R1, Yl, Y2, m, n, and m have the same meanings as above. (Production method D) General formula (X) [In the formula, Rr, Yl, Y2, m, n% R2 and R3 have the same meanings as above, and Re represents a lower alkyl group. ] By deacylating the compound represented by the following general formula [wherein R1, Yl, Y2, m, n, Rz and R3
has the same meaning as above. ] A method for producing an ether compound shown by.

More specifically, the compound represented by the above general formula (X) can be mixed with an alcohol solvent such as methanol or ethanol, an ether solvent such as tetrahydrofuran or 1,4-dioxane, or water or water and the above alcohol or ether solvent. In a mixed solvent of, in the presence of a base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium alcolade, potassium carbonate, etc., at room temperature to the boiling point of the solvent used, it is produced by reacting for 1 to 72 hours. I can do it. Also, in the above solvent, in the presence of an acid such as hydrochloric acid or sulfuric acid, at room temperature to 100°C,
It can also be produced by reacting for 8 hours.

In addition, in (the above-mentioned production method D), the compound represented by the general formula (X) can be produced, for example, by the route shown below.

[In the formula, R1, Y1% Y2, m, n, R2, R4, R5
, R6 and M have the same meanings as above. ] (Production method E) [In the formula, 21R1 and A have the same meanings as above. ] A compound represented by the general formula [wherein Y1%Yz, m and n have the same meanings as above. [In the formula, z, R1, Yl 1Y2 , m and n have the same meanings as above. ] A method for producing an ether compound shown by.

More specifically, the compound represented by the above general formula (XI) is mixed in an aprotic polar solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, 1,8-dimethylimidazolidinone, or In the absence of a solvent, a base such as sodium hydride, potassium hydride, potassium t-butoxy,
In the presence of potassium carbonate, sodium hydroxide, potassium hydride, etc., and in the presence of copper catalysts such as cuprous chloride, cuprous bromide, cuprous iodide, copper powder, copper acetate, cupric chloride, etc. at 100° C. to 200° C. for 1 hour to 48° C., preferably under an inert gas atmosphere such as nitrogen gas, under or in the absence of
It can be produced by reacting with a compound represented by the general formula (X[). In addition, in the above production method (E), the compound represented by the general formula (X[) can be produced, for example, by the route shown below.

[2% during the ceremony! and A have the same meanings as above.

] Some of the compounds that can be manufactured by the above (manufacturing corporation-E) are illustrated below.

6-phenoxy-2-pyridylmethyl neopentyl ether 6-(4-chlorophenoxy)-2-pyridylmethyl
Neopentyl ether 6-(4-bromophenoxy)-2-pyridylmethyl
Neopentyl ether 6-(4-fluorophenoxy)-2-pyridylmethyl Neopentyl ether 6-(4-methylphenoxy)-2-pyridylmethyl
Neopentyl ether 6-(4-ethylphenoxy)-2-pyridylmethyl
Neopentyl ether 6-(4-propylphenoxy)-2-pyridylmethyl Neopentyl ether 6-(4-1-butylphenoxy)-2-pyridylmethyl Neopentyl ether 6-(4-n-butylphenoxy)-2- Pyridylmethyl Neopentyl ether 6-(4-methoxyphenoxy)-2-pyridylmethyl Neopentyl ether 6-(4-ethoxyphenoxy)-2-pyridylmethyl Neopentyl ether 6-(4-propyloxyphenoxy)-2-pyridyl Methyl neopentyl ether 6-(4-methyl-2-
Bromophenoxy)-2-pyridylmethyl neopentyl ether 6-(4-methyl-2-chlorophenoxy)
-2-pyridylmethyl neopentyl ether 6-(2
,4-dichlorophenoxy)-2-pyridylmethyl Neopentyl ether 6-(4-chloro-2-fluorophenoxy)-2-pyridylmethyl Neopentyl ether 6-(4-bromo-2-fluorophenoxy)-2-
Pyridylmethyl Neopentyl ether 6-(4-bromo-2-methylphenoxy)-2-pyridylmethyl Neopentyl ether 6-(2,6-dichlorophenoxy)-2-pyridylmethyl Neopentyl ether 6-(
2,6-difluorophenoxy)-2-pyridylmethyl Neopentyl ether 6-(2,4-difluorophenoxy)-2-pyridylmethyl Neopentyl ether 6-phenoxy-5-fluoro-2-pyridylmethyl
Neopentyl ether 6-(4-chlorophenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(4-bromophenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(4-fluorophenoxy )-5-fluoro-2-
Pyridylmethyl Neopentyl ether 6-(4-methylphenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(4-ethylphenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(4- propylphenoxy)-5-fluoro-2-
Pyridylmethyl neopentyl ether 6-(4-1-
butylphenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(4-n-butylphenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(4-methoxyphenoxy)-5-fluoro- 2-Pyridylmethyl neopentyl ether 6
-(4-ethoxyphenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(4-propyloxyphenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(4-methyl-2-bromo phenoxy)-5-fluoro-2-pyridylmethyl neopentyl ether 6-(4-methyl-2-chlorophenoxy)-5-fluoro-2-pyridylmethyl neopentyl ether 6-(2,4-dichlorophenoxy)-5 -Fluoro-
2-pyridylmethyl neopentyl ether 6-(4-
10-2-fluorophenoxy)-5-fluoro-2
-Pyridylmethyl Neopentyl ether 6-(4-bromo-2-fluorophenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(4-bromo-2-methylphenoxy)-5-fluoro-2-pyridyl Methyl neopentyl ether 6-(2,6-dichlorophenoxy)-5-fluoro-
2-pyridylmethyl neopentyl ether 6-(2,
6-difluorophenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-(2,4-difluorophenoxy)-5-fluoro-2-pyridylmethyl Neopentyl ether 6-phenoxy-2-pyridylmethyl 2,2 .2-Trichloroethyl ether 6-(4-chlorophenoxy)-2-pyridylmethyl
2.2.2-Trichloroethyl ether 6-(4-bromophenoxy)-2-pyridylmethyl 2,2.2-Trichloroethyl ether 6-(4-fluorophenoxy)-2-pyridylmethyl 2,2.2- Trichloroethyl ether 6-(4-methylphenoxy)-2-pyridylmethyl 2,2.2-trichloroethyl ether 6-
(4-ethylphenoxy)-2-pyridylmethyl 2,
2.2-) Dichloroethyl ether 6-(4-methoxyphenoxy)-2-pyridylmethyl 2,2.2-Trichloroethyl ether 6-(4-chloro-2-fluorophenoxy)-2-pyridylmethyl 2,2 .2-Trichloroethyl ether 6-(2,6-dichlorophenoxy)-2-pyridylmethyl 2,2.2-Trichloroethyl ether 6-(2
,6-difluorophenoxy)-2-pyridylmethyl
2,2.2-trichloroethyl ether 6-(2,4-
(difluorophenoxy) -2-HIJ dimethyl 2
,2.2-)-dichloroethyl ether 6-phenoxy-5-fluoro-2-pyridylmethyl 2-chloro-2
-Methylpropyl ether 6-(4-chlorophenoxy)-5-fluoro-2-pyridylmethyl 2-bromo-
2-Methylpropyl ether 6-(4-bromophenoxy)-5-fluoro-2-pyridylmethyl 2-chloro-2-methylpropyl ether 6-(4-fluorophenoxy)-5-fluoro-2-
Pyridylmethyl 2-methyl-2-methoxypropyl ether 6-(4-methylphenoxy)-2-pyridylmethyl
2-Chloro-2-methylpropyl ether 6-(4-methoxyphenoxy)-5-fluoro-2-pyridylmethyl 2-chloro-2-methylpropyl ether 6-(4-chloro-2-fluorophenoxy)-2- Pyridylmethyl 2-bromo-2-methylpropyl ether 6-(4-bromo-2-fluorophenoxy)-2-pyridylmethyl 2-chloro-2-methylpropyl ether 6-(2,6-difluorophenoxy)-5- Fluoro-2-pyridylmethyl 2-chloro-2-methylpropyl ether 6-(2,4-difluorophenoxy)-2-pyridylmethyl 2-bromo-2-methylpropyl ether 6-phenoxy-5-fluoro-2-pyridyl methyl
2,2.2-)-dichloroethyl ether 6-(4-chlorophenoxy)-5-fluoro-2-pyridylmethyl 2,2.2-trichloroethyl ether 6-(4-bromophenoxy)-5-fluoro- 2-pyridylmethyl 2-methoxy-2-methylpropyl ether 6 2-pyridylmethyl 2-methoxy-2-methylpropyl ether 6-(4-methylphenoxy)-5-fluoro-2-pyridylmethyl 2,2.2- Trichloroethyl ether 6-(4-methoxyphenoxy)-5-fluoro-2-
Pyridylmethyl 2,2.2-trichloroethyl ether 6-(4-bromo-2-fluorophenoxy)-5-fluoro-2-pyridylmethyl 2,2.2-)dichloroethyl ether 6-(4-bromo-2 -methylphenoxy)-5-fluoro-2-pyridylmethyl 2,2.2-)dichloroethyl ether 6-(2,6-dichlorophenoxy)-5-fluoro-
2-pyridylmethyl 2,2.2-trichloroethyl ether 6-(2,6-difluorophenoxy)-5-fluoro-2-pyridylmethyl 2,2.2-trichloroethyl ether 6-(2,4-difluorophenoxy )-5-fluoro-2-pyridylmethyl 2,2.2-)-dichloroethyl ether 6-(4-chloro-2-fluorophenoxy)-5-fluoro-2-pyridylmethyl 2,2.2-)dichloro Ethyl ether 8-anilino-4-fluorobenzyl Neopentyl ether 8-(4-chloroanilino)-4-fluorobenzyl
Neopentyl ether 8-(4-fluoroanilino)-4-fluorobenzyl Neopentyl ether 8-(4-bromoanilino)-4-fluorobenzyl
Neopentyl ether 8-(4-methylanilino)-4-fluorobenzyl
Neopentyl ether 8-(4-ethylanilino)-4-fluorobenzyl
Neopentyl ether 8-(4-n-propylanilino)-4-fluorobenzyl Neopentyl ether 8-(4-i-propylanilino)-4-fluorobenzyl Neopentyl ether 8-(4-n-butylanilino) -4-fluorobenzyl Neopentyl ether 8-(4-methoxyanilino)-4-fluorobenzyl Neopentyl ether 8-(4-ethoxyanilino)-4-fluorobenzyl Neopentyl ether 8-(4-difluoromethoxyanilino) lino)-4-fluorobenzyl neopentyl ether 8-(4-pentafluoroethoxyanilino)-4-fluorobenzyl neopentyl ether 3-(4-chloro-2-fluoroanilino)-4-fluorobenzyl neopentyl ether 8-(4-chloro-2-methylanilino)-4-fluorobenzyl Neopentyl ether 3-(4-bromo-2-fluoroanilino)-4-fluorobenzyl Neopentyl ether 3-(4-bromo-2-methylanilino) )-4-fluorobenzyl neopentyl ether 8-(2,4-dimethylanilino)-4-fluorobenzyl neopentyl ether 8-(2,4-dichloroanilino)-4-fluorobenzyl neopentyl ether 8-( 2.4-difluoroanilino)-4-fluorobenzyl Neopentyl ether 8-(2.4-difluoroanilino)-4-fluorobenzyl Neopentyl ether 8-(2.6-dichloroanilino)-4-fluoro Benzyl neopentyl ether 8-(2-chloro-6-fluoroanilino)-4-
Fluorobenzyl neopentyl ether 3-anilino-4-fluorobenzyl 2.

2,2-trichloroethyl ether 8-(4-chloroanilino)-4-fluorobenzyl
2,2.2-Trichloroethyl ether 8-(4-fluoroanilino)-4-fluorobenzyl 2,2.2-Trichloroethyl ether 8-(4-bromoanilino)-4-fluorobenzyl
2,2.2-Trichloroethyl ether 8-(4-methylanilino)-4-fluorobenzyl
2,2.2-Trichloroethyl ether 3-(4-ethylanilino)-4-fluorobenzyl 2,2.2-trichloroethyl ether 8-(4-methoxyanilino)
-4-fluorobenzyl 2,2.2-trichloroethyl ether 8-(4-chloro-2-fluoroanilino)
-4-fluorobenzyl 2,2.2-)dichloroethyl ether 3-(4-chloro-2-methylanilino)-4-fluorobenzyl 2,2.2-trichloroethyl ether 3-(4-bromo-2-fluoro anilino)-4-fluorobenzyl 2,2.2-trichloroethyl ether 8-(2,4-difluoroanilino)-4-fluorobenzyl 2.2.2-trichloroethyl ether 8-(
2,6-difluoroanilino)-4-fluorobenzyl 2,2.2-)dichloroethyl ether 8-(2,6
-dichloroanilino)-4-fluorobenzyl 2,2
．． 2-trichloroethyl ether 3-(2-chloro-6
-fluoroanilino)-4-fluorobenzyl 2,2
．． 2-Trichloroethyl ether 3-anilino-4-fluorobenzyl 2-chloro-2
-Methylpropyl ether 8-(4-chloroanilino)-4-fluorobenzyl
2-Bromo-2-methylpropyl ether 8-(4-fluoroanilino)-4-fluorobenzyl 2-methoxy-2-methylpropyl ether 8-(4-bromoanilino)-4-fluorobenzyl 2-chloro-2- Methylpropyl ether 8-(4-methylanilino)-4-
Fluorobenzyl 2-methoxy-2-methylpropyl ether 8-(4-methoxyanilino)-4-fluorobenzyl 2-chloro-2-methylpropyl ether 8
-(4-difluoromethoxyanilino)-4-fluorobenzyl 2-chloro-2-methylpropyl ether8-(4-chloro-2-fluoroanilino)-4-fluorobenzyl 2-methoxy-2-methylpropyl ether 8-(2,4-difluoroanilino)-4-fluorobenzyl 2-chloro-2-methylpropyl ether 8-(2,6-difluoroanilino)-4-fluorobenzyl 2-chloro-2-methylpropyl ether 8-(2.6-dichloroanilino)-4-fluorobenzyl 2-methoxy-2-methylpropyl ether 8-(2-chloro-6-fluoroanilino)-4-fluorobenzyl 2-methoxy-2-methyl Propyl ether 8-(4-trifluoromethoxyanilino)-4-fluorobenzyl Neopentyl ether 8-(4-trifluoromethoxyanilino)-4-fluorobenzyl 2,2.2-trichloroethyl ether 8-anilino Benzyl Neopentyl ether 8-7 Nilinobenzyl 2,2.2-1 Lichloroethyl ether 8-phenoxy-4-fluorobenzyl Neopentyl ether 8-phenoxy-4-fluorobenzyl 2,2.2-
Trichloroethyl ether 8-phenoxy-4-fluorobenzyl 2-chloro-
2-Methylpropyl ether 3-(4-chlorophenoxy)-4-fluorobenzyl Neopentyl ether 8-(4-bromophenoxy)-4-fluorobenzyl Neopentyl ether 8-(2,8,4,5.6- (pentafluorophenoxy)-4-fluorobenzyl neopentyl ether 8-(2,8,4,5.6-pentafluoroanilino)
-4-Fluorobenzyl neopentyl ether Examples of the compounds of the present invention produced based on the above production method are shown below in Table 1, but the compounds of the present invention are not limited to these examples.

Table 1 Example 1 Synthesis of Compound (1) by Production Method (1) Under a nitrogen stream, 190 η of sodium hydride (68% oil dispersion) was mixed with dry dimethylformamide (hereinafter referred to as
It is abbreviated as dry DMF. ) Add to 80d. Add 1.02% of 6-phenoxy-2-pyridinemethanol to this in dry DMF.
(5sj) After adding the solution, the mixture was heated to 40-50℃ for 3
Heat for 0 minutes. Thereafter, a dry DMF (5sj) bath solution containing 1.20 P of neopentyl tosylate was added to the mixture at room temperature, and the mixture was heated at 50° C. for 1 hour and then cooled to room temperature.

The reaction solution was poured into ice water, 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 (developing solvent: n-hexane:ethyl acetate = 80:1) to obtain 0.811 of the target compound.

n':"1.5286 NMR data δ value (deuterochloroform solvent, TM8 internal standard) 0.98 (s, 9H) 8.20 (8,2f() 4.51 (s, 2H) 6.52~7 .72 (m, 8H) Example 2 Synthesis of compound (4) by production method (2) In a dry acetone bowl, 1.07 g of 2-chloromethyl-6-fethoxypyridine and 1 g of 2,2.2-trichloroethanol were added. .69P was added, and to this was added 1.69P of potassium carbonate.
575' is added, and heating and refluxing is continued for 86 hours under nitrogen flow. After cooling the reaction solution to room temperature, it was poured into ice water and extracted twice with diethyl ether. The ether layers were combined and washed with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. leave The residue was subjected to silica gel column chromatography (developing solvent: n-hexane:ethyl acetate = 50:1) to obtain the target compound 260.

nr-at 567 O NMR data δ value (deuterated chloroform solvent, TM8
internal standard) 4.20 ('1.2H) 4.81
(S, 2H) 6.80-7.82
(m, 8H) Example 8 Compound (7) according to production method (0)
) Synthesis of 2-methallyloxymethyl-6-fethoxypyridine O,'tsy was mixed with 20 dl of auto-acid, and hydrogen chloride gas was blown into it for 80 minutes under ice-cooling.

Next, 60 ml of toluene was added to the reaction solution, and the mixture was cooled with water for 5 ml.
% sodium hydroxide aqueous solution, and separate the toluene layer. After drying the toluene layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain the target compound 810 (developing solvent: n-hexane:ethyl acetate = 80:1).

nD 1.5461 NMR data δ value (deuterated chloroform solvent.

TM8 internal standard) 1.60 (S, 6H) 8.59 (8, 2H) 4.60 (S, 2H) 6.60-7.80 (m, 8H) Example 4 Compound ( Synthesis of 1) Under a nitrogen stream, 881η of sodium hydride (63% oil dispurge) was added.
Add to 60yzl of dry DMF. To this is added a solution of 0.889% of 2,2-dimethylpropertool in dry DMF (5d) and the reaction mixture is heated to 50-60°C for 80 minutes. Thereafter, 2-chloromethyl-6-fethoxypyridine 2.049 (Dry DMF (5 ml) was added to this at room temperature.
) Add molten H, heat the reaction at 506C to 60C for 1 hour, and then continue stirring at room temperature all day and night. The reaction solution was poured into 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 using a developing solvent; n-
Hexane:ethyl acetate=8'0: IL Target compound 2,18y was obtained.

1 1.5284 NMR data δ value (M chloroform solvent, TM8 internal standard) 0.98 (S, 9fi) 8.20 (S, 2H) 4.51
(S, 2H) 6.5-7.7 (m, 8H) Example 5 Synthesis of compound (2) according to production method 0 8-(N
-acetylanilino)-4-fluorobenzyl 1.57 of neopentyl ether, 10 of methanol and 8 of water
ml of mixed solution, and add 1.8 mL of potassium hydroxide to this solution.
Added 7. The reaction solution was heated to 60°C to 65°C and continued stirring for 12 hours. After cooling the reaction solution to room temperature, water and ether were added to separate the layers, the aqueous layer was extracted once with ether, the ether layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and then extracted under reduced pressure. The solvent was distilled off, and the residue was subjected to silica gel column chromatography (developing solvent: n-hexane:ethyl acetate = 3021) to obtain 0.96 y of the desired product as an oil.

n, 1.5522 NMR data δ value (deuterated chloroform solvent, TM8 internal standard) 0.98 (s, 9H) 8.11 (S, 2H) 4.47 (S, 2flI) 5.70-5.
90 (b, IH) 6.80-7.50 (m,
8H) Example 6 Synthesis of compound (3) according to production method (1) Under a nitrogen atmosphere, 0.82F of sodium hydride (60% oil disbarge) was dried in dimethylformamide 2
0 m, and 0.755' of phenol was added thereto at room temperature. After the generation of hydrogen gas has stopped, the temperature is further increased to 40°C.
Continue stirring at ~50°C for 80 minutes. The reaction solution was cooled to room temperature, 2.2 g of 3-bromo-4-fluorobenzyl neopentyl ether was added thereto, 500 mV of anhydrous cuprous chloride was added, and the mixture was heated at 140°C to 145°C for 8 hours. continued to react. After cooling the reaction solution, water and ether were added to disperse it, the aqueous layer was extracted once with ether, the ether layers were combined, and washed in the order of 5% aqueous hydrochloric acid, 10% aqueous sodium hydroxide, and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (opening solvent: n-hexane: ethyl acetate = 50:1) to obtain 1.12 of the target compound. Obtained.

n's'' 1.5197 NMR data δ value (N chloroform solvent, TMS internal standard) 0.88 (5,9H) 8.08 (B, 2H) 4.40 (S, 2H) 6.713-7. 50 (m, 8H) Example 7 Synthesis of compound (A) according to production method ① Under a nitrogen atmosphere, sodium hydride (60% 0% oil disparity run, 22
F was placed in 20 portions of dry dimethylformamide, and 0.61 F of p-cresol was added thereto. Heat the reaction solution to 50°C
The mixture was heated to 60°C and the reaction was continued for 30 minutes.

The reaction solution was cooled to room temperature, and 1.2 y of 6-chloro-2-pyridylmethyl neopentyl ether was added thereto, followed by 200 μm of anhydrous cuprous chloride. The reaction solution was heated to 180 ml.
The reaction was continued for 5 hours by heating to ~140°C. Thereafter, the same operation as in Example 6 was performed to obtain 0.41 mm of the target compound.

r+%” 1,5 f311 NMR data δ value (deuterated chloroform bath medium, TM8 internal standard) 0.95 (s, 9H) 2.86 (S, 8H) 8.15 (S, 2H) 4.45 (S , 2H) 6.80-7.80 (m, 7H) Example 8 Synthesis of compound 0(a) by production method (to) 3-(N-acetyl-4-chloroanilino)-4-fluorobenzyl neopentyl ether 0.69 was dissolved in 10 g of methanol, and 800 ml of potassium hydroxide and 2 ml of water were added thereto.

The reaction was continued at 60°C for 5 hours. Thereafter, the same operation as in Example 5 was performed to obtain the target compound 0.487.

n"7" 1.5648 NMR data δ value (deuterochloroform solvent, TMS internal standard) 0.91 (s, 9H) 8.10 (S, 2H) 4.42 (S, 2H) 5.70-5. 90(b, IH) 6.80-7.45(m, 7J Example 9 Production method (q) Synthesis of compound (c) 3-phenoxy-4-fluorobenzyl methallyl ether 0.
659 was dissolved in 15 ml of methanol, and at room temperature,
0.84 F mercuric acetate was added. After continuing the reaction at room temperature for a day and night, the reaction solution was cooled to 0 to 5°C, and 0.87 y of potassium hydroxide and 0.0 y of sodium borohydride were added to it.
．． 259 was added. The reaction solution was filtered through Celite, water and ether were added to the P solution to separate the layers, and the ether layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Developing solvent for silica gel column chromatography; n-hexane: ethyl acetate =
10=1), the desired compound 820■ was obtained.

n”7”1.5289 NMR data δ value (deuterochloroform solvent, TM8 internal standard) 1.20 (S, 6H) 8.21 (S, 8H) 8.40 (8,2H) 4.41 (s, 2H) 6.71-7.52 (m, 8H) Example 10 Synthesis of compound (c) according to the production method (Production method) In a nitrogen atmosphere, 160η of sodium hydride (60% oil disvergence) was dried in dimethylformamide. 20
ml, add neopentyl alcohol 360T9 to this
and heat at 506C to 60C for 30 minutes. When the generation of water system has stopped, the reaction solution is cooled on ice, and 1.07 g of 6-(4-bromophenoxy)-2-chloromethylpyridine is added to it.
Add. The reaction was continued at room temperature for 1 hour, and then heated to 50°C and further continued for 8 hours. After pouring the reaction solution into ice water, the same operation as in Example 4 was performed to obtain the target compound 0.42P.

1.5476 NMR data δ value (deuterochloroform solvent, TM8 internal standard) 0.97 (S, 9H) 3.17 (s, 2H) 4.48 (8, 2H) 6.72-7.89 ( m, 7EI) When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, it may be used as it is without adding any other ingredients, but it is usually used in the presence of a solid carrier, liquid carrier, or gaseous carrier. carrier, surfactant,
It can be mixed with other formulation auxiliaries, feed, etc., or it can be made into an emulsion by impregnating base materials such as incense sticks and mats.

It is formulated and used in wettable powders, powders, granules, oils, aerosols, heated fumigants such as mosquito coils and electric mosquito mats, fogging agents such as fogging, non-heated fumigants, poison baits, etc.

These preparations contain o, oi% to 95% by weight of the compound of the present invention as an active ingredient.

The solid carriers used include fine powders 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. Alternatively, granules may be mentioned, and liquid carriers include aliphatic hydrocarbons such as kerosene and kerosene, and aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene.

Halogenated hydrocarbons such as dichloroethane, trichloroethylene, carbon tetrachloride, methanol, etc.

Ethanol, isopropanol, ethylene glycol,
Alcohols such as cellosolve, ketones such as acetone, methyl ethyl ketone, cyclohexanone, isophorone, ethers such as diethyl ether, dioxane, tetrahydrofuran, esters such as ethyl acetate, nitrites such as acetonitrile, isobutyronitrile, acids such as dimethylformamide, dimethylacetamide, etc. Examples include vegetable oils such as amide, dimethyl sulfoxide, soybean oil, and cottonseed oil. Examples of the gaseous carrier include chlorofluorocarbon gas, LPG (liquefied petroleum gas), dimethyl ether, and the like. Surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate salts, alkyl (aryl) sulfonate salts,
Anionic surfactants such as dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester. Formulation aids such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, tl[, casein, gelatin, CMO, (
(carboxymethylcellulose) 1 pine oil, agar, etc.; stabilizers include alkyl phosphates such as PAP (isopropyl acid phosphate) and TCP (tricresyl phosphate); vegetable oil; , BEI
Examples include antioxidants such as T and BHA, fatty acid salts such as sodium oleate and calcium stearate, and fatty acid esters such as methyl oleate and methyl stearate.

Examples of formulations are shown below. In addition, the compounds of the present invention are shown in Table 1 by the compound number at the time of recording. Parts are parts by weight.

Formulation Example 1 0.2 part of the compound of the present invention (2), (8) or (4), 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 2 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 20 parts of the present compound (2), (3) or (7), 10 parts of fenitrothion, 8 parts of calcium ligninsulfonate
1 part, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrated silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 4 1 part of the compound of the present invention (2), (8) or (8), 2 parts of carbaryl, 87 parts of kaolin clay, and 10 parts of talc
Thoroughly grind and mix these parts to obtain a powder.

Formulation Example 5 5 parts of the present compound (2), (8) or (to), 1 part of synthetic hydrated silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 62 parts of kaolin clay were thoroughly ground and mixed, and water was added. After adding and kneading well, the mixture is granulated and dried to obtain granules.

Formulation Example 6 Compound of the present invention (1)% (2) or (8) 0.05
0.2 parts of tetramethrin, 0.05 parts of resmethrin, 7 parts of xylene, and 32.7 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, and a valve part is attached. An aerosol is obtained by filling 60 parts of petroleum gas under pressure.

Formulation Example 7 Compound of the present invention (1), (2) or (8) 0.8
P is d-trans primary chrysanthemum acid ester of allethrin 0.3
7, dissolve it in methanol 20w1, mix it evenly with mosquito repellent Kagawa carrier (mixing tab powder: lees powder: wood flour in the ratio of 8:5:1) 99.4 and stir. After evaporating the compound methanol, add 150 ml of water, mix well, mold and dry to obtain each mosquito coil.

These preparations are used as they are or diluted with water. In addition, other insecticides, acaricides, nematicides, fungicides,
When used in combination with herbicides, plant growth regulators, fertilizers, soil conditioners, etc., the application rate is usually 5 to 5,009 kg/10 are, and emulsions, hydrating agents, etc. are diluted with water. When applied, the application concentration is toppm to 1
000 pl)m, and powders, granules, oils, aerosols, etc. are applied as a preparation without any dilution.

Next, a test example is shown. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Structural Formula Name Test Example 1 Rice stems (length about 12 cI11) were soaked for 1 minute in a water dilution of an emulsion of the present invention compound and control compound below prepared according to Formulation Example 2 at a predetermined concentration. Soaked. After air-drying, put the rice stems in a test tube and inject one adult leafhopper of the resistant strain.
0 animals were released, and 1 day later, they were examined to see if they were alive or dead, and the LCso value (50%
(lethal concentration) was determined (two replicates).

The results are shown in Table 8.

Table 8 Test Example 2 Rice stems (length about 121 mm) were immersed for 1 minute in a water dilution of an emulsion of the present invention compound and a control compound obtained according to Formulation Example 2 at a predetermined concentration. After air-drying, the rice stems were placed in a test tube and 10 adult brown planthoppers were released. One day later, they were examined to see if they were alive or dead, and the LC50 value (50% lethal concentration) was determined.
2 repetitions).

The results are shown in Table 7.

Table 9 Test Example 8 Rice stems (length: about 121 cm) were immersed for 1 minute in a water dilution of an emulsion of the present invention compound and control compound obtained according to Formulation Example 2 at a predetermined concentration. After air-drying, the rice stems were placed in a test tube and 10 brown planthopper adults were released, and one day later, they were examined to see if they were alive or dead, and the LOso value (50% lethal concentration) was determined.
2 repetitions).

The results are shown in Table 5.

Table 5 Test Example 4 Attach a filter paper of the same size to the bottom of a polyethylene cup with a diameter of 5.5 CIM. An emulsion of the following compound and a control compound prepared according to Formulation Example 2 was diluted with water to a predetermined degree.
．． 7- was dropped onto the filter paper, and sucrose 80119 was evenly added as bait. Release 10 adult female house flies into it.
After 48 hours with the lid closed, check the formation and check the LCso value (5
0% lethal concentration) was determined (2 replicates).

The results are shown in Table 6.

Table 5 Test Example 5 The following compounds of the present invention and control compound were diluted with acetone, and the diluted solution was mixed with an inner diameter of 1g and a height of 3c. The drug amount is 78TI9 at the bottom of the 11 aluminum dish (bottom area 78.5-).
/m'' and air-dried.Next, 10 adult German cockroaches (5 males and 5 males) were released onto the treated surface of the aluminum dish and forced into contact with it.

After 24 hours of contact, the test insects were collected in a new container, fed with water and food, and 72 hours later, their survival was determined to determine the mortality rate (2 repetitions).

The results are shown in Table 1.

Test Example 6 A 200-fold dilution (500 ppm
Equivalent) 2g7 was impregnated into 18F artificial food for Spodoptera japonica and placed in a polyethylene cup with a diameter of 113.

Ten 4th instar larvae of Spodoptera were released into the larvae, and 6 days later, their survival and death were examined (2 repetitions).

The results are shown in Table 6.

Table 8 Test Example 7 -
10 adult female spider mites per leaf, 2
It was stored in a constant temperature room at 5°C. After 6 days, a 200-fold dilution (equivalent to 5 ooppm) of the following emulsion of the present invention compound and control compound in water prepared according to Formulation Example 2 was sprayed at 15 g per pot on a turntable, and at the same time 2 ml was sprinkled on the soil JIIn. I noted it. Eight days later, the degree of damage caused by spider mites to each plant was investigated.

The criteria for determining effectiveness is And so.

The results are shown in Table 9.

Table q.

Claims (7)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X represents an oxygen atom or a group represented by the formula -NH-, and when X represents an oxygen atom, Z represents a nitrogen atom or a group represented by the formula - It represents a group represented by CH=, and when X represents a group represented by the formula -NH-, Z represents a group represented by the formula -CH=. When X represents an oxygen atom and Z represents a nitrogen atom, and when X represents a group represented by the formula -NH-, R_1 represents a hydrogen atom or a fluorine atom, X represents an oxygen atom, and Z represents a group represented by the formula -NH-. When representing a group represented by -CH=, R_1 represents a fluorine atom. Y_1 and Y_2 are the same or different, a hydrogen atom,
It represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, or a haloalkoxyl group, and m and n each represent an integer of 1 to 4, the sum of which is 5 or less. R_2 represents a methyl group or a chlorine atom, and R_3 represents a methyl group, a halogen atom or a methoxy group. ] An ether compound represented by (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z represents a nitrogen atom or a group represented by the formula -CH=, and when Z represents a nitrogen atom, R_1 is a hydrogen atom or a fluorine atom. represents an atom,
When Z represents a group represented by the formula -CH=, R_1 represents a fluorine atom. Y_1 and Y_2 are the same or different, a hydrogen atom,
It represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, or a haloalkoxyl group, and m and n each represent an integer of 1 to 4, the sum of which is 5 or less. A represents a halogen atom. ] Compounds and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_4 represents a methyl group or a chlorine atom. ] A general formula characterized by reacting an alcohol compound represented by the following in the presence of a base ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z, R_1, Y_1, Y_2, m, n and R
_4 has the same meaning as above. ] A method for producing an ether compound shown by. (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z represents a nitrogen atom or a group represented by the formula -CH=, and when Z represents a nitrogen atom, R_1 is a hydrogen atom or When a fluorine atom is represented and Z represents a group represented by the formula -CH=, R_1 represents a fluorine atom. Y_1 and Y_2 are the same or different, a hydrogen atom,
It represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, or a haloalkoxyl group, and m and n each represent an integer of 1 to 4, the sum of which is 5 or less. ] Compounds and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, Y represents a halogen atom, tosyloxy group, or mesyloxy group. ] A general formula characterized by reacting a compound represented by in the presence of a base ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z, R_1, Y_1, Y_2, m and n are the same as above. have meaning. ] A method for producing an ether compound shown by. (4) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X represents an oxygen atom or a group represented by the formula -NH-, and when X represents an oxygen atom, Z represents a nitrogen atom or a group represented by the formula - It represents a group represented by CH=, and when X represents a group represented by the formula -NH-, Z represents a group represented by the formula -CH=. When X represents an oxygen atom and Z represents a nitrogen atom, and when X represents a group represented by the formula -NH-, R_1 represents a hydrogen atom or a fluorine atom, X represents an oxygen atom, and Z represents a group represented by the formula -NH-. When representing a group represented by -CH=, R_1 represents a fluorine atom. Y_1 and Y_2 are the same or different, a hydrogen atom,
It represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, or a haloalkoxyl group, and m and n each represent an integer of 1 to 4, the sum of which is 5 or less. ] and the general formula HR_5 [wherein R_5 represents a chlorine atom, a bromine atom, or a methoxy group. ] A general formula characterized by reacting with a compound represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, has. ] A method for producing an ether compound shown by. (5) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 represents a hydrogen atom or a fluorine atom,
Y_1 and Y_2 are the same or different, a hydrogen atom,
It represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, or a haloalkoxyl group, and m and n each represent an integer of 1 to 4, the sum of which is 5 or less. R_2 represents a methyl group or a chlorine atom, R_3 represents a methyl group, a halogen atom or a methoxy group, and R_
6 represents a lower alkyl group. ] A general formula characterized by deacylation reaction of the compound represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, Y_1, Y_2, m, n, R_2 and R_3 have the same meaning as above. has. ] A method for producing an ether compound shown by. (6) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z represents a nitrogen atom or a group represented by the formula -CH=, and when Z represents a nitrogen atom, R_1 is a hydrogen atom or When a fluorine atom is represented and Z represents a group represented by the formula -CH=, R_1 represents a fluorine atom. A represents a halogen atom. ] Compounds represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc.
It represents an alkoxyl group or a haloalkoxyl group, and m and n each represent an integer of 1 to 4, the sum of which is 5 or less. ] A general formula characterized by reacting a phenol derivative represented by the following in the presence of a base ▲ There are mathematical formulas, chemical formulas, tables, etc. have the same meaning. ] A method for producing an ether compound shown by. (7) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X represents an oxygen atom or a group represented by the formula -NH-, and when X represents an oxygen atom, Z represents a nitrogen atom or a group represented by the formula - It represents a group represented by CH=, and when X represents a group represented by the formula -NH-, Z represents a group represented by the formula -CH=. When X represents an oxygen atom and Z represents a nitrogen atom, and when X represents a group represented by the formula -NH-, R_1 represents a hydrogen atom or a fluorine atom, X represents an oxygen atom, and Z represents the formula When representing a group represented by -CH=, R_1 represents a fluorine atom. Y_1 and Y_2 are the same or different, a hydrogen atom,
It represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, or a haloalkoxyl group, and m and n each represent an integer of 1 to 4, the sum of which is 5 or less. R_2 represents a methyl group or a chlorine atom, and R_3 represents a methyl group, a halogen atom or a methoxy group. ] An insecticide and acaricide characterized by containing an ether compound represented by the following as an active ingredient.