WO1994017048A1

WO1994017048A1 - Oxadiazole derivative

Info

Publication number: WO1994017048A1
Application number: PCT/JP1994/000070
Authority: WO
Inventors: Takashi Kishimoto; Kaoru Noda; Yasushi Shibata; Michihiko Matsuda; Renpei Hatano; Makio Yano; Takao Iwasa
Original assignee: Nippon Soda Co., Ltd.
Priority date: 1993-01-21
Filing date: 1994-01-20
Publication date: 1994-08-04

Abstract

A compound having excellent insecticidal and acaricidal effects and represented by general formula [I] wherein Q represents (a) or (b); X represents halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, nitro, amino optionally substituted by C1-C3 alkyl, or C1-C3 haloalkyl; r1 and r2 represent each independently hydrogen, C1-C3 alkyl, hydroxy, halogen, thiocarbamoyl optionally substituted by C1-C3 alkyl, thiocarbamoyloxy optionally substituted by C1-C3 alkyl, C1-C3 alkoxycarbonyloxy, C1-C3 alkoxy, -S(O)nr3 (wherein n represents an integer of 0 to 2, and r3 represents C1-C3 alkyl), amino optionally substituted by C1-C3 alkyl, or C1-C3 alkylcarbonyloxy, or alternatively r1 and r2 may be combined together to represent oxo, hydroximino, C1-3 alkoxy-imino or methylene; and Y1, Y2, Y3, Y4 and Y5 represent each independently hydrogen, C1-C6 alkyl, C1-C10 alkoxy, C1-C6 alkylthio, halogen, amino optionally substituted by C1-C3 alkyl, or hydroxy; provided that when either Y2 or Y4 is not t-butyl, then Y3 represents t-butyl, neopentyl, t-butoxy, t-butylthio or t-butylamino.

Description

Specification

Oxadiazole derivative

Technical field:

The present invention relates to a novel oxadiazole derivative and an insecticide and acaricide. Background technology:

Many insecticides and acaricides have been used in the past, but their efficacy was insufficient, their use was limited due to drug resistance problems, and phytotoxicity and contamination of plants occurred. However, because of their high toxicity to humans and fishes, many of them are not necessarily satisfactory control agents. Therefore, there is a demand for the development of a drug that can be used safely with few such disadvantages.

Japanese Patent Application Laid-Open Publication No. Hei 11-261381 (EP 2 735 344) describes compounds having acaricidal activity and related to the compound of the present invention. For example, the following compounds are described. is there.

However, there is no description of the insecticidal activity in this specification.

DISCLOSURE OF THE INVENTION:

An object of the present invention is to provide an insecticide and acaricide that is effective and can be used safely.

As a result of various studies, the present inventors have found that at least one ortho position of a phenyl group directly bonded to an oxaziazole ring is substituted with a fluorine atom, and On whether or para position with a t one butyl group at the meta position of Fuweniru group attached through a zone Ichiru ring carbon atoms - A_ C ₄ H ₈ ¹ (wherein, Alpha is an oxygen atom, a sulfur atom, A compound having an amino group, a methylene group, or a bond) has a high activity not only in the susceptible ticks but also in the resistant ticks, and furthermore has an excellent insecticidal activity. The present invention has been completed.

That is, the present invention provides a compound represented by the general formula (I):

(Where Q is

X is a halogen atom, d-3 alkyl group, ₃ alkoxy group, 3 alkyl Chiomoto, nitro group, C, - ₃ alkyl optionally substituted amino group with a group, or C, -3 haloalkyl group;

r 1 and r 2 are each independently a hydrogen atom, a Ct- ₃ alkyl group, a hydroxy group, a halogen atom, a thiocarbamoyl group optionally substituted with Ci- ₃ alkyl,

C, -3 alkyl optionally substituted Chio carbamoyl O alkoxy group, CI- ₃ alkoxides aryloxycarbonyl O alkoxy group, _d-3 alkoxy, -S (0) "r 3 ( wherein n is 0 Represents an integer of 2 and r ₃ represents a d- ₃ alkyl group), an amino group optionally substituted with ₃ alkyl, or a d-3 alkylcarbonyloxy group, or

, R! > R ₂ is together in a go-between Okiso group, human Dorokishii Mi amino group, C - ₃ alkoxy Lee Mi amino group, or a methylene group!;

_{_{, Y 2, Y 3, Y}} 4 and Upsilon ₅ each represents a hydrogen atom, ds alkyl group,

—,. Alkoxy groups, C, - ₆ alkylthio group, a halogen atom, with CI- ₃ alkyl An amino group or a hydroxyl group which may be substituted;

However, when Y ₂ or Upsilon ₄ is not t-butyl group, Y ₃ is t _ butyl group, neo-pentyl group, t-butoxy group, or t- Puchiruchio group, shows the t-Puchiruami cyano group. ] The compound represented by the formula, its manufacturing method and insecticides and acaricides.

The production method of the compound of the present invention is as follows.

Manufacturing method 1

Wherein ha 1 represents a _{_{halogen, X, Y 1, Y 2}} , Y 3, Y 4, Y 5, r!, R 2 are as defined above. The reaction is carried out in an organic solvent, if necessary, in the presence of a base, for 1 hour to several 10 hours, from −20 ° C. to the boiling point of the solvent used. As the solvent, DMF, acetonitril, THF, benzene, chloroform, dioxane and the like can be used. As the base, pyridine, triethylamine, DBU, sodium hydride, sodium hydroxide, sodium carbonate and the like can be used. Manufacturing method 2

_{_{X,, Υ 2, Υ 3}} , Υ 4, Υ 5,, r 2 are as defined above. The reaction is carried out in an organic solvent from 50 ° C. to the boiling point of the solvent used, for 1 hour to several 10 hours. DMF, toluene, xylene, dichlorobenzene and the like can be used as the solvent.

Manufacturing method 3

Y ₃

In the formula, ha 1 represents a halogen, and X, Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , r,, r

2 has the same meaning as described above. The reaction is carried out in an organic solvent, if desired, in the presence of a base.

It is carried out for 1 hour to several 10 hours from 20 ° C. to the boiling point of the solvent used. As the solvent, DMF, acetonitril, THF, benzene, chloroform, dioxane and the like can be used. As the base, pyridine, triethylamine, DBU, sodium hydride, sodium hydroxide, sodium carbonate and the like can be used. Manufacturing method 4

Manufacturing method 5

In, Q, X, Y _{_{formula, Y 2, Y 4, Y}} 5, r, r 2 is as defined above -. Zeta oxygen atom, a sulfur atom and - shows the ΝΗ group. The reaction is carried out in an organic solvent, optionally in the presence of a catalyst, from 100 ° C. to the boiling point of the solvent used, for 1 hour to several 10 hours. As the solvent, dichloromethane, DMF, acetonitril, THF, chloroform and the like can be used. As the catalyst, trifluoromenosulfonic acid, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid and the like can be used.

Manufacturing method 6

Further, the compound of the present invention depends on the type of the substituent, It can also be produced by appropriately selecting similar reactions. Wherein _{ha 1, QX,, Y 2} , Y 3, Y 4, Y 5, r! , r ₂ have the same meaning as described above. a)

r 3 r 4 represents a lower alkyl group.

b)

C)

r ₅ and r _{6 each} represent a d alkyl group.

O, s e Trilimi S d

o

r represents a C, _-3 alkyl group, d alkylcarbonyl group, Ci-alkoxy group, or a thiocarbamoyl group which may be substituted with C alkyl.r ₈ and r _{9 each} represent an alkyl group; Shows oxygen, sulfur, and nitrogen atoms. e)

r is _t representing a C i- ₃ alkyl group

f)

r _{1 D} represents a C alkyl group. g)

r H represents a C ₃ alkyl group ₍

h)

r ₁₂ is C!-,. Shows an alkyl group.

When the reaction is carried out by any of the methods, the target product can be obtained by performing ordinary post-treatment after the reaction.

The structure of the compound of the present invention was determined from IR, NMR, MS and the like. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described in more detail by way of examples.

Reference example 1

Dissolve 3.8 g of N-hydroxy-1-2-chloro-6-fluorobenzamidine in 30 ml of acetate tritium, and add pyridine 2.0 at 0 ° C and 4.3— Butylphenylacetyl chloride 4.3 g was added while maintaining the reaction temperature at 0 ° C. After stirring at 0 ° C. for 30 minutes and then at room temperature for 2 hours, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and filtered, and then ethyl acetate was distilled off under reduced pressure. The obtained residue was separated and purified by a silica gel column to obtain 5.2 g of the desired N- (4-t-butylphenylacetic acid) _2-chloro-6-fluorobenzamidine.

Example 1

Dissolve 5.2 g of N- (4-tert-butylphenylacetoxy) 1-2-chloro-6-fluorobenzamidine in 10 ml of N, N-dimethylformamide and add 150 The mixture was stirred at ° C for 2 hours. After cooling, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and filtered, and then ethyl acetate was distilled off under reduced pressure. The obtained residue was separated and purified by a silica gel column to give the desired 5- (4-t-butylbenzyl) -13- (2-chloro-6-fluorophenyl) 1-1,2,4-oxadiazol (Compound No. 1) ) 4.7 g were obtained. η. ²² - ⁴ 1.5438 Reference Example 2

1.5 g of N-hydroxyl 4-t-butylphenylacetamide was dissolved in 15 ml of acetonitrile, 0.7 g of pyridine at 0 ° C, and then 2-chloro 6 one full O Robben benzoyl click port Lai de 1.2 hours after stirring at 3 0 minutes and then room temperature for a 4 g reaction temperature at _c 0 ° C was added while maintaining 0 ° C, the reaction mixture was poured into ice water, acetic acid After extraction with ethyl ester, washing with water, drying over magnesium sulfate, and filtration, ethyl acetate was distilled off under reduced pressure. The obtained residue was separated and purified by a silica gel column to obtain 2 g of the desired N- (2-chloro-6-fluorobenzoyloxy) -141-tert-butylphenylacetamide. Example 2

N— (2-chloro-1-6-benzobenzoyloxy) 1-4—t—Butylphenylacetamidine 2 g dissolved in N, N-dimethylformamide 10 ml 1 at 150 ° C for 2 hours Stirred. After cooling, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and the ethyl acetate was distilled off under reduced pressure. The obtained residue is separated and purified by a silica gel column, and the desired 3- (4-t-butylbenzyl) -1-5- (2-chloro-6-fluorophenyl) 1-1,2,4-oxaziazol (compound number) 1.67) 1.5 g were obtained. η. ²² ° 1.5499 Example 3

1.5 g of 2-hydroxy-6-fluorobenzamidine Preliminarily, 23 g of sodium metal was dissolved in 10 ml of a methanol solution to dissolve, and then 2.0 g of methyl 4-ethoxy-3-t-butylphenyl acetate was added, followed by 12 hours. Heated to reflux. After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and filtered, and then ethyl acetate was distilled off under reduced pressure. The obtained residue was separated and purified by a silica gel column, and the desired 5- (4-ethoxy-3-t-butylbensyl) -13- (2-chloro-1-6-fluorophenyl) -1,1,2,4-oxadiazole ( Compound No. 65) 0.4 g was obtained. n _D ^{24 2} 1.5454

Example 4

Dissolve 2.2 g of 3- (4-hydroxybenzyl) -1-5- (2-chloro-1-6-fluorophenyl) -1,2,4-oxadiazole in 40 ml of dichloromethane and prepare a catalytic amount of trifluorene. After adding methanesulfonate (0.11) and cooling to —78, isobutene (10.0 g) was blown in for 5 minutes. Three hours later, the temperature was gradually returned to room temperature. After 2 hours at room temperature, a large excess of triethylamine was added to the reaction solution, which was poured into ice water, the organic layer was separated, washed with water, dried over magnesium sulfate, and filtered. The residue obtained by distilling off the dichloromethane under reduced pressure is separated and purified using a silica gel column, and the desired 3- (4-hydroxy-3-t-butylbenzyl) -1-5- (2-chloro-1-6-) 0.75 g of (fluorophenyl) -1, 2,4-oxadiazole (compound No. 228) was obtained. mp 1 1 9— 1 2 1 ° C Example 5

3- (4-Hydroxy-3-tert-butylbenzyl) -1-5- (2-chloro-6-fluorophenyl) _1,2,4-oxoxadiazole 0.75 g to acetonitrile 30 m 1 To the dissolved solution, anhydrous potassium carbonate (0.32 g) and iodide chill (0.5 g) were added and heated to reflux. After 5 hours, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate and filtered. The residue obtained by distilling off the ethyl acetate under reduced pressure is separated and purified by a silica gel column to obtain the desired 3- (4-ethoxy-3-t-butylbenzyl) -1-5- (2-chloro-1-6-) Fluorophenyl) -1,2,4-oxadiazole (Compound No. 2 12) 0.43 g was obtained. n _D ^{22 5} 1.5501

Reference example 3

After dissolving 1.9 g of 4-t-butoxyphenylacetic acid in 15 ml of tetrahydrofuran, 1.5 g of carbonyldimidazole was added at room temperature, and after confirming foaming, the mixture was stirred for 30 minutes. The solution was previously prepared with N-hydroxy-2-chloro-6 1.7 g of fluorobenzamidine and 1.lg of triethylamine were added dropwise at room temperature to a solution of 15 ml of tetrahydrofuran in which lg was dissolved, and reacted overnight. The reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and filtered, and then ethyl acetate was distilled off under reduced pressure. The obtained residue was separated and purified using a silica gel column to obtain 1 g of the desired N- (4-t-butoxyphenylacetoxy) -2-chloro-opening-6-fluoro-benzamidine.

Example 6

-(4-t-butoxyphenylacetoxy) Dissolve 1 g of 1-chloro-6-fluorobenzomidine in 15 ml of N, N-dimethylformamide at 150 ° C for 2 hours Stirred. After cooling, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and the ethyl acetate was distilled off under reduced pressure. 0.6 g of 5- (4-t-butoxybenzyl) -13- (2-chloro-6-fluorophenyl) 1-1,2,4-oxadiazole (compound No. 93) was obtained. n _D ²³ - ⁸ 1.5328 Example 7

Dissolve 1.6 g of 3- (4-hydroxybenzyl) _5— (2_chloro mouth_6-fluorophenyl) -1,2,4-oxadiazol in 30 ml of dichloromethane, A catalytic amount of trifluoromethanesulfonic acid (0.1 g) was added, and after cooling to 178 ° C, 2.0 g of isobutene was blown in over a few minutes. After 3 hours, add 0% to the reaction solution.

1 g of triethylamine was added, and the temperature was gradually returned to room temperature. The reaction solution was poured into ice water, the organic layer was separated, washed with water, dried over magnesium sulfate, and filtered. Dichloromethane was distilled off under reduced pressure, and the residue obtained was separated and purified using a silica gel column.

0.35 g of (4-t-butoxybenzyl) -15- (2-chloro-6-fluorophenyl) 1-1,2,4-oxoxadazole (Compound No. 240) was obtained. mp 4 2-4 3 ° C

Example 8

Dissolve 3.1 g of 5- (4-t-butylbenzyl) -3- (2-chloro-6-fluorophenyl) —1,2,4-oxadazole in 50 ml of dioxane and 3 ml of water Further, 3.3 g of selenium dioxide was added at room temperature, and the mixture was refluxed. After cooling to room temperature, the reaction solution was poured into water, insolubles were filtered off using celite, extracted with ethyl acetate, washed with water, dried over magnesium sulfate and filtered, and ethyl acetate was distilled off under reduced pressure. The obtained residue is separated and purified by a silica gel column,

5- (4-t-Butylbenzoyl) -13- (2-chloro-16-fluorophenyl) 1-1,2,4-oxoxadiazole (Compound No. 5) 2.22 was obtained. 111 6 0—

6 3 ° C Example 9

5- (4-t-butylbenzyl) -3- (2-chloro-6-fluorophenyl) 1 1,2,4-oxadiazole 1 g with N, N-dimethylformamide 10 m The mixture was dissolved in 1 and 0.1 g of 60% sodium hydride was gradually added at 0 ° C. After stirring for 2 hours while maintaining the reaction temperature at 0 ° C, 0.55 g of methyl iodide was added dropwise. One hour later, the mixture was returned to room temperature and stirred for 4 hours. The reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and filtered. The resulting residue is separated and purified by a silica gel column, and the desired 5- (α-methyl-41-t-butylbenzyl) -13- (2-chloro-6_fluoro-mouth phenyl) —1,2,4-oxa 0.5 g of diazole (Compound No. 2) was obtained. n 24.2

D 1.5344

Example 10

5-(4-t-butylbenzyl)-3-(2-chloro-6-fluorophenyl) 1, 1, 2, 4-oxadiazole 1 g is dissolved in N, N-dimethylformamide 10 ml and 0 °. 0.14 g of 60% sodium hydride with C was gradually added. After stirring for 1 hour while maintaining the reaction temperature at 0 ° C, 0.22 g of paraformaldehyde was added. After 1 hour, return to room temperature and stir overnight, then pour the reaction mixture into ice water and add ethyl acetate. After extraction with an ester, washing with water, drying over magnesium sulfate and filtration, ethyl acetate was distilled off under reduced pressure. The resulting residue was separated and purified using a silica gel column, and the desired 5 — (a, α-methylene-1 4 — t — butylbenzyl) _ 3 — (2 —chloro-6 —fluorophenyl) — 1, 2, 4 0.7 g of oxadazole (Compound No. 6) was obtained. n _D ^25. ⁵ 1.5256

Example 1 1

5-(4-t-butylbenzyl) 1-3-(2-chloro-6-fluorophenyl)-1, 2,4-oxadiazole 1 g is dissolved in THF 10 ml and potassium t-butoxide is added at room temperature. 39 g was added and stirred. Three hours later, 0.41 g of isoamyl nitrate was added and reacted. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and filtered, and then ethyl acetate was distilled off under reduced pressure. The obtained residue is separated and purified using a silica gel column, and the desired 5 — (a, α-hydroxymino 1 4 _ t — butylbenzyl) 1 3 — (2 —chloro 6-fluorophenyl) — 1 0.4 g of 2,2,4-oxadiazole (Compound No. 7) was obtained. η. ^25, ⁵ 1.5068

Example 1 2

5 — (4 t-butyl benzyl) _ 3 _ (2 — black mouth — 6 _ fluorophenyl) 1 g of 1,2, · 4-oxadiazole was dissolved in 10 ml of N, N-dimethylformamide, and 0.14 g of 60% sodium hydride was gradually added at 0 ° C. After stirring for 1 hour while maintaining the reaction temperature at 0 ° C, 0.23 g of methyl isothiocyanate was added, and the mixture was returned to room temperature and further stirred overnight. The reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and then ethyl acetate was distilled off under reduced pressure. The obtained residue is separated and purified by a silica gel column, and the desired 5-C- (N-methylthiolrubamoyl) -14-t-butylbenzyl] —3— (2-chloro-1-6-fluorophenyl) 1-1 0.4 g of 2,2,4-oxadiazole (Compound No. 9) was obtained. η. ^25, ⁵ 1.5546

Example 13

5— (41 t-butylbenzoyl) —3— (2_chloro-6-fluorophenyl) -1,2,4—oxadiazole 4.0 g was dissolved in 30 ml of dry getylether under a stream of nitrogen. — At 0 ° C, 20 ml of methylmagnesium bromide was added and stirred. Two hours later, 60 ml of 2N sulfuric acid was gradually added at −70 ° C., the temperature was returned to room temperature, the reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, and filtered, and ethyl acetate was distilled off under reduced pressure. The obtained residue was separated and purified by a silica gel column to give the desired 5- (a-hydroxy-1-a). 2.6 g of methyl-4-t-butylbenzyl) -3- (2-chloro-16-fluorophenyl) 1-1,2,4-oxadiazole (Compound No. 4) was obtained. n _D ²² - ⁷ 1.5514 Example 14

5-(α-Hydroxy α-methyl 4-t-butylbenzyl) 13- (2-chloro-6-fluorophenyl) 1,1,2,4-oxadiazole 0.7 g of benzene It was dissolved in 15 ml, 0.9 g of getylaminosulfur trifluoride (DAST) was added, and the mixture was refluxed for 30 minutes. After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate, washed with water, dried over magnesium sulfate, and filtered, and then ethyl acetate was distilled off under reduced pressure. The obtained residue was separated and purified using a silica gel column, and the desired 5- (a-fluoro-a-methyl-41-t-butylbenzyl) -13- (2-chloro-16-fluorophenyl) 1-1, 0.6 g of 2,4-oxadazole (compound number 17) was obtained. n _D ²² - ⁵ 1.5287 Example 1 5

5- (4-t-butoxybenzyl) -1-3- (2-chloro-6-fluorophenyl) — 1,2,4-oxadiazol 3.4 g dissolved in 20 ml of acetic acid, room temperature Under ice cooling, 2.0 g of chromic anhydride was added and reacted at room temperature. Two hours later, the reaction solution was poured into water, extracted with ethyl acetate, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate, washed with water, dried over magnesium sulfate, filtered, and the ethyl acetate was distilled off under reduced pressure. Separation and purification using a column, the desired 5- (4-t- Toxibenzoyl) -1- (2-chloro-6-fluorophenyl) -1,2,4-oxadiazole (Compound No. 97) (2.0 g) was obtained. mp 4 2— 4 4 ° C Example 16

5-(4-t-butoxybenzoyl) 1-3-(2-chloro-6-fluorophenyl)-1,2, 4-oxadiazole 5.7 g is dissolved in ethyl alcohol 5 Om 1 and 0 ° C. Then, 0.4 g of sodium borohydride was gradually added. Two hours later, the reaction solution was poured into ice water, extracted with chloroform, washed with water, dried over magnesium sulfate, and filtered. The resulting residue was separated and purified using a silica gel column, and the desired 5- (α-hydroxy_4_t-butoxybenzyl) —3— (2-cyclomouth_6—fluorophenyl) 1-1,2, 4-oxadiazole (Compound No. 95) 4. Og was obtained. η. ²² · ⁹ 1.5423

Example 17

5-(α-hydroxyl 4-t-butoxybenzyl) 1-3- (2-chloro-6-fluorophenyl) 1-1,2,4-oxadiazole 1. Dissolve Og in dichloromethane 20 m1 After that, 26 g of pyridine and then 0.32 g of thionyl chloride were added at 120 ° C. After 2 hours, pour the reaction mixture into ice water, extract with dichloromethane, wash with water, dry over magnesium sulfate, filter, and distill off dichloromethane under reduced pressure. This gave 0.8 g of a crude oil of 5-(α-chloro- 4-t-butoxybenzyl)-1-(2-chloro-1-monofluorophenyl)-1, 2, 4-oxoxadiazole.

5- (α-chloro-1-4-butoxybenzyl) -1-3- (2-chloro-1-6-fluorophenyl) 1-1,2,4-oxoxadiazole 0.52 g of acetonitrile After dissolving in 10 ml, 0.3 g of a 30% solution of methylamine in ethanol was added at 120 ° C., and the mixture was returned to room temperature and stirred for a while. The reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and filtered, and then ethyl acetate was distilled off under reduced pressure. The resulting residue was separated and purified using a silica gel column, and the desired 5- (monomethylamino 4-t-butoxybenzyl) 1-3- (2-chloro-1-6-fluorophenyl) -1,2,4- 0.3 g of oxaziazole (Compound No. 107) was obtained. η. ²¹ '° 1.5413

Example 18

5- (4-t-Butylbenzoyl) -1-3- (2-Chloro-6-fluorophenyl) 1-1,2,4-oxadiazole 0.9 g and 2.4 g of getylaminosulfur trifluoride (DA ST) After stirring the mixture at 70 ° C while maintaining the reaction temperature, the reaction mixture was poured into ice water, extracted with ethyl acetate, and saturated. After washing with sodium bicarbonate water, washing with water, drying over magnesium sulfate, and filtration, ethyl acetate was evaporated under reduced pressure. The resulting residue is separated and purified by a silica gel column to give the desired 5- (a, α-difluoro-4-t-butylbenzyl) -1,3- (2-chloro-6-fluorophenyl) -1,1,2,4-oxaziazo One liter (compound No. 16) of 0.8 g was obtained. n _D ²³ - ² 1.5217

Example 19

0.6 g of 5- (α-hydroxy-1 4-t-butylbenzyl) -13- (2-chloro-6-fluorophenyl) 1-1,2,4-oxadiazol was dissolved in 10 ml of dichloromethane. Thereafter, 0.16 g of pyridine and 0.16 g of acetyl chloride were added under ice cooling. After stirring at room temperature for 2 hours, the reaction solution was poured into ice water, extracted with dichloromethane, washed with water, dried over magnesium sulfate, filtered, and the dichloromethane was distilled off under reduced pressure. The resulting residue is separated and purified using a silica gel column to give the desired 5- (α-acetoxy-41-t-butylbenzyl) _3- (2-chloro-6-fluorophenyl) —1,2,4-oxadiazole (compound No. 10) 0.4 g was obtained. n 25. S

D 1.4825

Example 20

(α-hydroxyl 4-t-butylbenzyl) 1-3- (2-chloro-6 After dissolving 0.6 g of (fluorophenyl) -1,2,4-oxadiazole in 10 ml of dichloromethane, 0.16 g of pyridine and 0.22 g of ethyl chloroformate were added under ice-cooling. After stirring at room temperature for 2 hours, the reaction solution was poured into ice water, extracted with dichloromethane, washed with water, dried over magnesium sulfate, filtered, and then dichloromethane was distilled off under reduced pressure. The resulting residue was separated and purified using a silica gel column to give the desired 5- (α-ethoxycarbonyloxy-4-t-butylbenzyl) —3- (2-chloro-6-fluorophenyl) —1, 0.4 g of 2,4-oxadiabul (Compound No. 12) was obtained. η. ²⁵ ^'5 1.4827

Example 2 1

5-(α-hydroxy-14-t-butylbenzyl) 1-3- (2-chloro-1-6-fluorophenyl) 1-1,2,4-oxaziazol 0.6 g of benzene 10 m

After dissolving in water, 0.17 g of triethylamine and then 0.15 g of methyl isothiocyanate were added under ice-cooling. After stirring overnight at room temperature, the reaction solution was poured into ice water, extracted with benzene, washed with water, dried over magnesium sulfate, filtered, and benzene was distilled off under reduced pressure. The obtained residue is separated and purified by a silica gel column to obtain the desired 5-[[alpha]-(メチル -methylthiophenyrubamoyloxy) -14-t-butylbenzyl] 13- (

0.2 g of 2-chloro-6-fluorophenyl-11,2,4-oxaziazol (Compound No. 11) was obtained. n _D ²⁵ · ⁵ 1.5368 Example 22

5-(α-hydroxy-4t-butylbenzyl) 13- (2-chloro-6-fluorophenyl) -1,2,4-oxadiazole 0.8 g to N, N-dimethylformamide 10 m1 It was dissolved and 0.1% of 60% sodium hydride was gradually added at 0 ° C. After stirring for 1 hour while maintaining the reaction temperature at 0 ° C, 0.41 g of methyl iodide was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and filtered, and then ethyl acetate was distilled off under reduced pressure. The resulting residue was separated and purified using a silica gel column to give the desired 5- (α-methoxy-14-t-butylbenzyl) -13- (2-chloro-16-fluorophenyl) —1,2 0.3 g of, 4-oxadiazole (Compound No. 13) was obtained. n _D ²⁵ · ⁵ 1.4839

Reference example 4

OCOMe

5- (α-chloro-4-acetoxybenzyl) 1-3- (2-chloro-6-fluorophenyl) 1-1,2,4_oxaziazol 6.88 At 30 ° C, 8.4 g of methylthiol sodium salt (15% aqueous solution) was added. After stirring at room temperature, the reaction mixture was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and dichloromethane was distilled off under reduced pressure. did. The obtained residue is separated and purified by a silica gel column, and the desired 5 — (α-methylthio-14-acetoxybenzyl) _ 3 _ (2 _ 1-6-fluorofuryl) — 1, 2, 4 — 5.1 g of oxaziazole was obtained.

Reference example 5

Dissolve 3.9 g of 5- (α-methylthio-14-acetoxybenzyl) -13- (2-chloro-16-fluorophenyl) 1-1,2,4-oxadiazole in 30 ml of methanol. Then, add 4.1 g of potassium carbonate dissolved in 15 ml of water under ice-cooling, stir at room temperature for 30 minutes, concentrate methanol under reduced pressure, adjust the pH to 4 with dilute hydrochloric acid, and then add acetic acid. Extracted with ethyl ester. The organic layer was washed with water, dried over magnesium sulfate, filtered, and ethyl acetate was distilled off under reduced pressure to give 5- (α-methylthio-4-hydroxybenzyl) 13- (2-chloro-16-fluoro 3.3 g of phenyl) 1-1,2,4-oxoxadiazole were obtained.

Example 23

Dissolve 4.5 g of 5- (α-methylthio-14-hydroxybenzyl) -13- (2-chloro-6-fluorophenyl) -11,2,4-oxaziazol in 40 ml of dichloromethane and prepare a catalyst. An amount of trifluoromethanesulfonic acid (0.2 g) was added and, after cooling to −20, 7.0 g of isobutene was blown in over a few minutes. 1 o'clock After stirring at a temperature of 10 ° C. to −20 ° C., the mixture was cooled to 50 ° C., and 0.3 g of triethylamine was added to the reaction solution, and the temperature was gradually returned to room temperature. The residue obtained by evaporating the reaction solution under reduced pressure is separated and purified by a silica gel column, and the desired 5- (α-methylthio-4-1t-butoxybenzyl) -13- (2-chloro-6-fluorophenyl) 1-1 3.5 g of 2,2,4-oxadiazole (Compound No. 104) was obtained.

n 24.5

D 1.5450

Example 2 4

5- (α-methylthio-1 4-t-butoxybenzyl) 1-3- (2-chloro-1-6-fluorophenyl) 1-1,2,4-oxaziazol 0.5 g in dichloromethane 5 m 1 After dissolving in water, 0.3 g of metabenzo-perbenzoic acid was added under ice-cooling. After stirring at room temperature for 2 hours, the reaction solution was distilled off under reduced pressure, and the resulting residue was separated and purified using a silica gel column to obtain the desired 5- (α-methylsulfinyl 4-t-butoxybenzyl). 0.35 g of one 3- (2-chloro-1-6-fluorophenyl) _1,2,4-oxaziazole (Compound No. 105) was obtained. η. ^25, ⁵ 1.5478

Example 2 5

5- (H-methylthio 4-t-butoxybenzyl) 1-3- (2-Chloro-16-fluorophenyl) 1,1,4-oxadiazole 0.5 g After dissolving the solution in 5 ml, 0.6 g of metabenzo-perbenzoic acid was added under ice-cooling. After stirring at room temperature for 2 hours, the reaction solution was distilled off under reduced pressure, and the residue obtained was separated and purified using a silica gel column to obtain the desired 5_ (α-methylsulfonyl 4-t-butoxybenzyl). — 3— (2_chloro-16-fluorophenyl) -11,2,4—oxaziazole (Compound No. 106) 0.4 g was obtained. n _D ²⁵ - ² 1.5271

Representative examples of the compounds of the present invention including the above Examples are shown in Tables 1 and 2.

Table 1

F X

Compound X Q r 1 r 2 Yn Physical constant

N-0 22.4

1 C1 HH 4- ⁴ Bu n _D 1.5438

24.2

2 〃〃 Me 〃 n _D 1.5344

24. 1

3 〃〃 OH 〃〃 n _D 1.5573

22. 7

4 〃〃 OH Me 〃 n _D 1.5514

5 〃〃 = 0 〃 mp.60- 63 ° C

25.5

6 〃〃 = CH ₂ 〃 n D 1.5256

25.5

7 〃〃 = Screen 〃 n _D 1.5068

8 〃〃 = N0Et 〃

25.5

9 〃〃 -CSNHMe H 〃 n _D 1.5546

10 〃〃 -OCOMe 〃〃 n _D '1.4825 Table 1 (Continued) Y 0 r Yn Physical number

N— 0

11 11 \ ー门 Factory SNHMP H n _D '1.5368 0 〃〃〃〃

丄 1 Otoshi n _D 1.4827 lo -UMe n _D 1.4839

14 -NHMe

Fifteen

Q

16 F

17 Me n _D 1.5287

18 UH lit n _D 1.5427 iwe iwe

20 〃〃 SMe H 〃

21 〃 SOMe 〃

22 〃 H 〃〃

F Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued) 1 Object TJY o Vn

1 1 1 I ii object * T J theory IH. 3C No.

N-0

Λ 1 II \ n u

ΌΌ 丄丄 n Π Ulit, D DI, 4 Dll Π 丄 * D4 o

Entering

ft

61 F 〃 H 〃

62 CI 〃 2, 5-F ₂ , 4- Bu ft

63 2, 5-Cl ₂ , 4- Bu

O

64-c 5 * n

-Then 1 t

, 4-D B.u.

65 〃 3-Bu, 4-OEt n 丄, 5454

66 Me 〃 ft

0 / OH VIS. Ul 1

68 〃〃〃 Me 〃

69 〃〃 = 0 〃 mp.103-105 ° C

70 〃〃 = CH ₂ Table 1 (continued) «B3 a

Λ n W r 1 r Vr

2 I n rf½ I

ffi

N-0

71 11 II \ = ■ trj.,

Entering

70 D ^

Di H H fi

lo 1 π π

74 ff 〃〃

75 fl 〃〃 tf

CH3

76 CF ₃ 〃〃 tt

O L end UMe 〃〃 ff

0 Me 〃〃 ff

7Q ff

I U2 〃〃

80 CI 〃〃〃 3- ^l Bu

81 〃 ft 〃 ft 3- tBu, 4-OH mp.141-142 ° C

23.5

82 ft 〃〃〃 3- tBu, 4-OMe n _D 1.5543 Table 1 (continued)

(Continued)

(Continued) b 1 Compound X nw Yn Physical constant

¾

N-0

1071 — recitation 1 H1

Entering

1ΛΟ

Γ

no Me

111 Me

ll2 FHH n D 1.5377 ll3 Me n _D 1.5274

114 OH

丄 1 丄 1 Me 卹 96_98 ° C

116 = 0

117 = CH ₂

118 = Marauder Table 1 (continued)

ΐ ^ 6 <If / lD _< I Table 1 (continued)

1 Vn

J 口 v π W Γ l Γ 2 n Dimensions J f Wfi ^ 1 ¾

N— 0

1 then i u n u 4, 4 Dll

Entering

25.5 丄 44 0 4-n U n 1.5 ^ 99

22.0 r

145 L b -to 2, 4-U riD 1.5318

146 2, 6-F ₂ , 4-0 Bu

23.5

147, 5-F2, 4-0 Bund 1.5185

27. 5

14ο Z, d-shi, 4-U 1.5510

149 t) One, 12, 4 ~ U Bu Vis. Ui 1

b,

150 ff 〃 c p n t

— Then 12, 4-U f ff

丄 1 f

iD 丄 Ot 0 then 2, 4

152 〃〃〃 4-CH ₂ 'Bu n _D 1.5449

153 〃 Me 〃〃

154 〃〃 OH 〃〃〃 0 = 〃 991

〃 HO S9T

HO 〃

〃〃〃

H H 〃〃 291

〃 0 = 〃〃 ΐ9ΐ

HO 〃 09ΐ

〃〃 HO 〃〃 69ΐ

〃〃 8ST ng H H 〃丄 SI

Οο90ΐ-50ΐ "din 〃 0 = 99ΐ

HO YV 13 ς ς ςτ

0-N

蓥蓥[呦 u people 2 J ■ j b X

(? C) Halla Ϊ

ε f L00Q / 6 d £ / lDd mLl IP6 OAV Table 2

n

X

Compound X Q r r Yn Physical constant number

0-N

167 C1 HH 4-'Bu n _D 1.5499

168 〃〃 Me 〃〃 n _D 1.5517

169 〃 OH mp.99-100 ° C

170 〃〃〃 Me 〃

171 〃〃 = 0 〃 mp.70-71 ° C

172 〃〃 = CH ₂ 〃

173 〃〃 = N0H

174 〃〃 = N0Et 〃

175 〃〃 F H 〃

176 〃〃 CI 〃〃 H 3 Customer 88T

〃丄 8ΐ

0 = 98ΐ

% η 'ΐ ^α u 〃〃〃 98ΐ

9 '93

Οοδ6-Ζ6 · * π HO HO 〃 8ΐ

69 ^^ 'ΐ ^α u 9 £ 8ΐ

Q 'Q Ζ

〃 Ζ8ΐ

〃 I ΐ8ΐ

H H 8 08ΐ

〃〃 3 〃 6 丄 I

〃 81ΐ. IS-6 'din ά i i / 13 丄丄 1

N-0

蓥 u input & X 呦 ^

9 f6df / XDJ 8fO, l / f6 OAV (Continued)

Y

J Λ Γ l Γ ffe

2 V I n n 10 J7I

J W ΐϊ Ίand ¾Χ. No.

0-N

h

丄 r oUMe ri 4-DU

Entering

1 ΩΛ u fl ff

H3 し

1 π 1

lyi shito 3

1 n

VOL UMe

1 no

bMe ft

194 Νϋ ₂ ff

195 NH ₂ ft ff ff

丄 SJb I HMe

1 Q ff ff ft

丄 7

y / shi i ώ Γ, 4 DU

198 〃〃〃〃 3-F, 4-'Bu

22.2

199 〃〃〃〃 2_0Et, 4-tBu _D 1.5475

200 〃〃 Me 〃〃 Table 2 (continued) Compound X n 1 Γ Yn ¾ Ύ7I T ¾S † ιH ¾ 5ζr

0-N 22.2

201 p 1 \\ n n H Π D 丄.

20? Π 〃〃 3-0Et, 4- ^l Bu

ZU Me 〃 p Γ Π u 〃

23.9 one-to-one 1 2-OEt, 5-Cl, 4- ^l Bu n _D 1.5451

Me 〃 u / Γ n 〃

し shi 1 2-Me 4- tBu

2-OEt, 5-Br, 4- ^l Bu

210 〃〃 25-F ₂ , 4- ^t Bu

211 〃〃〃 2, 5-Cl ₂ 4-tBu

22.5

212 〃〃〃 3 Bu 4-OEt n _D 1.5501 Table 2 (continued) ィ Dragon compound XQ rr Yn Physical te number

0-N

213 CI, Me H 3- ^l Bu, 4-OEt n _D l. 5328

214 OH mp.H3-ll4 ° C

215 OH Me

216 = 0 mp.109-H0 ° C

217 = CH ₂

218 Br H H

219 I

220 F mp. 10l-103 ° C

221 Me

222 OH

223 Me

224 = 0 mp. 172-175 ° C Table 2 (continued) Compound χ Q r 1 ro Yn Physical constant number

O-N

l 3 / \\ 11 H 11 wn, 〃

007 then 1 t D ..

0- DU ib t nu

o- Bu, 4-UH mp.119-121 C D .. Π¾1

L o o- «

Bu, 4-UMe

d-Bu 4-U rr

n ^ n «

231 3-t n ..

Bu, 4-0 Pr f f

~ oil, 4-U Dll

〃 ft o_ _Dri

D, U, * / i_n unpen

234 〃〃〃〃 3- ^l Bu, 4-0 ⁿ 0ct

235 〃〃〃〃 5-tBu, 2-OMe

236 〃 ft ft 5- tBu, 2-OEt Table 2 (continued) Compound Λ rir Y n Number of landfills

0-N

L6 \ 1 person, enter Π n b-DU, -U rr-DU, -U rr

239 5-Bu 2-0 Bu

240 4-0 Bu mp.42-43 ° C

241 Me n _D 1.5415 a

242 OH

243 Me mp.124-125.5C

244 = 0

= CH ₂

246 = ■

247 -NOEt

248 -CSNHMe H (Continued) I A thing γ

1 す J J Γ Γ 1 V 2 V I n 11 i n n J W ¾ ^ 1 Ά

¾ "

0-Ν

1 \\ π A,

And I n 4— n Ut D

D, U

〃 -Π UΓshiΠ UΜiVlοfc! 〃

251 SMe

252 〃〃 SOMe 〃

253 S0 ₂ Me

254-picture e

255 〃〃 F 〃〃

256 〃〃〃 F 〃

257 〃〃〃 Me Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

匕 r i r 2 Yn u

¾ ■

0-Ν

J i 1 \\ OH H 4-CH Bu

OH Me

one = 0

297 H H CO

Me

299 OH

300 OH Me

301 = 0

H H 4-NH'Bu

303 Me

304 OH

305 Me Table 2 (continued) Compound XQ rr Yn Physical constant number

0-N

306 C1 person, input = 0 4-NH ^l Bu

The compound of the present invention has high activity against ticks resistant to known acaricides and also has high activity against pests such as aphids.

The compound of the present invention can be used for controlling agricultural pests, sanitary pests, grain storage pests, clothing pests, house pests, and the like.

Lepidopteran pests, for example, Hasmonyoto, Totoga, Tamanayaga, Aomushi, Tamanaginba, Konaga, Jyanokokakumonhamaki, Chiyamahamaki, Momomoshinguiga, Nashihime Shingui, Mikanhamoguriga, Chiyanohogaga, Machinaga Hemiptera pests, such as Kamiga moga, Kobnomimea, Yo-chi bitten corn borra, Amerika shirohitori, Sujimadarameiga, Heliotis spp., Helicobelpa spp., Aggrotis spp., Iga spp., Kodolinga spp. Plum aphid, Aphid aphid, Aphid aphid, Betula aeruginosa, Betula aeruginosa, Pterodactyla japonicus, Aphidina aphid, Anopheles japonicus, Aphrodite auricidae, Onshiko whitefly, Tobacco whitefly , Pear lice, pear grub beetles, brown beetle, brown beetle, cedar brown planthopper, black-tailed beetle, etc., Coleoptera, insects, for example, Kisujino beetle, beetle beetle, Colorado beetle, rice beetle, mosquito beetle, moss , Pterodactylus, Pterodactyla var. 'E, rice leaf blowfly, key mouth Drosophila melanogaster, sand flies, Koga takae power, Anetaishima power, Sinama medaka, etc. Hymenoptera, Thrips palmi, Thrips palmiflora, etc., Hymenoptera pests, for example, Diplomatidae, Japanese hornet wasps, Power Bumble Bees, etc., Orthoptera pests, for example, Japanese cockroaches, Black cockroaches, Black cockroaches, Tonosamabata, etc. Insect pests, for example, house termites, sarcophagid termites, etc., Lepidopteran pests, for example, rodents, lice, pests, for example, rodents, ticks, for example, mites, for example, Namihadani, Nisenamihadani, Kanzahadani, Citrus spider Ngoha Mite, mikansabidanii, lingosavidinii, tyrannid mite, brevipalpas. Tosentiyu, Rice Shingaresenchu, Matsunozai Senyu, etc.

The compounds of the present invention excellent killing adults effect, refreshing in insect effect, larvicidal effect, also _c shows the ovicidal effect, in recent years diamondback moth, © down force, Yokobai, organic Li emissions agent in aphid like many pests and mites, carbamate The development of resistance to drugs and acaricides has led to a problem of insufficient efficacy of these drugs, and drugs that are effective against pests and mites of resistant strains are desired. The compound of the present invention is an agent having an excellent insecticidal and acaricidal effect against not only susceptible strains but also pests and mites of organic phosphorus agents, carbamate agents, pyrethroid agents, and acaricide-resistant strains.

The insecticide and acaricide of the present invention contains the compound represented by the formula [I] as an active ingredient, and can be used as a pure product of the active ingredient compound. That is, they are used in the form of wettable powders, water solvents, powders, emulsions, granules, flowables and the like. As an additive and carrier, when a solid agent is intended, plant powders such as soybean flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, clay and other mineral powders, sodium benzoate, Organic and inorganic compounds such as urea and sodium sulfate are used.

For liquid dosage forms, vegetable oils, mineral oils, petroleum fractions such as kerosene, xylene and sorbent naphtha, sikglohexane, siquiloxaxanone, dimethylformamide, dimethylsulfoxide, trichloroethylene Use methyl isobutyl ketone, water, etc. as the solvent. In these preparations, a surfactant can be added if necessary to obtain a uniform and stable form. The wettable powders, emulsions, aqueous solutions and flowables obtained in this way are diluted to a certain concentration with water and used as suspensions or emulsions. Is done. It goes without saying that the compound of the present invention is effective alone, but it can also be used in combination with various insecticides, acaricides, nematicides, fungicides and synergists.

Representative examples of insecticides and acaricides that can be used by mixing with the compound of the present invention are shown below.

Organophosphorus and barbamate insecticides:

Fenthion, Phenyltrothion, Diazinone, Chlorpyrifos, ESP, N-Midothion, Fentrate, Dimethoate, Formothion, Marathon, Trichlorfon, Thiometone, Phosmet, Dichlorvos, Asephate, EPBP, methyl parathion, oxydimethonmethyl, ethione, salithion, cyanophos, isoxathion, pyridafunthion, hosalon, metidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphomethos, ethythiomethosphen , Pyraclophos, monocrotophos, azinphos-methyl, aldicarb, methomil, thiodicarb, carbofuran, carbosulfan, benfracarb, Rachiokarupu, Purobokisuru, B P M C, M T M C, M I P C, force Rubariru, pyrimidone mosquitoes one blanking, Echiofenkaru blanking, Fuenokishikarupu, Carta-up, thiocyclam, Bensuruta-up and the like.

Pyrethroid insecticides:

Permethrin, cypermethrin, deltamethrin, fueno <relate, fenproprin, pyrethrin, allesulin, tetramethrin, resmethrin, dimesulin, propasulin, pheno Trin, protoline, fulvalinate, cyflutrin, cyhalothrin, flucitrine, etofenprox, cycloprotoline, tolomethrin, silafluofen, profenprox, Clinatrine etc.

Benzoylurea and other insecticides:

Difluvenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, Pyridiproxyfen, methoprene, benzepin, diafenthiuron, imidac-prid, fipronil, nicotine sulfate, rotenone, methyl aldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses.

Nematicide:

Fenamiphos, phosthiazetate, etc.

Acaricide:

Chlorbenzylate, phenylisobromolate, dicophor, amitraz, BPPS, benzomate, hexithiax, phenbutazin oxide, polynactin, quinomeionate, CPCBS, tetradihon, avermectin, milbemectin, clofentezine, shihehe Xatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifene, penothiocalp, dienochlor, etc.

Fungicide:

Thiophane methyl, benomyl, carbendazole, thiabendazole, phorpet, thiuram, ziram, zineb, maneb, polycarbonate, IBP, EDDP, fusaride, probenazole, isoprothiolane, TPN, captan, polyoxin, Blastosaidin S, Kasugamycin, Streptomycin, Paridamidycin, Tricyclazole, Pyroquilon, Panazinoxide, Mepronil, Flutolanil, Pencyclon, Iprodione, Himexazole, Metaraxyl, Triflumizole, Trifolin, Triazimehon, Vitel Yunoru, fenarimol, propiconazole, simoxanil, prochloraz, difurazoate, hexaconazole, miclobutanil, diclomedine, techopen Phthalam, Provineb, Dithianon, Josetyl, Vinclozolin, Procymidone, Oxazixyl, Guazatine, Propamocalp hydrochloride, Fluazinam, Oxolinic acid, Hydroxydisoxazole, etc.

Next, examples of the preparation are shown, but the carrier, surfactant and the like to be added are not limited to these examples.

Example 26 Emulsion Compound of the present invention 10 parts Alkyl phenyl polyoxyethylene 5 parts

Dimethylformamide 50 parts

Xylene 3 5 parts

Mix and dissolve the above, dilute with water before use and spray as an emulsion.

Example 2 7 wettable powder

Compound of the present invention 10 parts

Higher alcohol sulfate 5 parts

Diatomaceous earth 80 parts

Silica 5 parts

The above mixture is mixed and pulverized into fine powder, diluted with water before use and dispersed as a suspension ₍ Example 28

5 parts of the compound of the present invention

Talc 9 4.7 parts

0.3 parts of silica

Mix and grind the above and spray as it is when using.

Example 2 9 granules

5 parts of the compound of the present invention

Cray 7 3 copies

Bentonite 20

Dioctyl sulfosuccinate sodium salt 1 part

1 part of sodium phosphate

Granulate the above and apply as it is when used.

Industrial applicability:

Test Example 1 Efficacy against Aphids

10 days after germination, seedlings sown in three-size pots were inoculated with iridescent aphid adults. One day later, the adult was removed, and the drug was applied to the cucumber parasitized by the produced nymphs. According to the formulation of the emulsion shown in Example 26 of the drug, a drug solution diluted with water was sprayed so that the compound concentration was 31 ppm. They were placed in a constant temperature room with a temperature of 25 and a humidity of 65%, and the insecticidal rate was examined after 6 days. The results are shown in Table 3 below.

^ 3 ^ fe

Compound 畨 "Insecticidation rate after 6 days (%)

1 1 0 0

1 0 1 0 0

1 6 1 0 0

2 2 1 0 0

2 3 1 0 0

6 5 9 0

8 2 1 0 0

9 3 1 0 0

1 2 8 1 0 0

1 3 0 1 0 0

1 3 5 1 0 0

1 5 1 0 0

2 7 6 1 0 0

Control compound A 6 7

"B 0

"C 17 Control compound A Control compound B

Control compound C

Test Example 2 Efficacy against red mites

An acaricide-resistant female adult of Citrus unshiu is placed on a tangerine leaf in a petri dish. After inoculation of 0 mice, a drug solution diluted with water was sprayed with a rotary spray tower according to the formulation of the emulsion described in Example 26 of the drug, so that the compound concentration became 31 ppm. Place in a constant temperature room at a temperature of 25 ° C and a humidity of 65%, remove the adults 3 days after spraying, and determine whether the eggs laid in the last 3 days have grown to adults. The eyes were examined to determine the acaricidal effectiveness *. The results are shown in Table 4 below.

T e + T l C e + C l

T e + TL C e + C L

* Acaricidal effectiveness (%) x 1 0 0

C e + C l

1-

C e + C L

T e: Number of dead eggs in the treatment area

T 1: Number of dead larvae in the treated area

TL: Number of larvae in the treatment area

C e: Number of dead eggs in untreated area

C 1: Number of dead larvae in untreated area

CL: Number of larvae in untreated area

Table 4

Compound number Acaricidal effectiveness (%) Compound number Acaricidal effectiveness (%)

1 Λ Λ 1 0 1 丄丄 U U 丄 0 9 Q

Ό 丄 ο 1 Λ Λ 1 0 C 1 0

L 丄 U U 丄 0 0 丄 π υ

1 Λ Λ 1 Λ Q Q

0 丄 U U 丄 4 U ο 0

1 7 1 Λ Λ 1 λ 1

丄 i 丄 U U 丄 4 丄丄 Π U υ o 0 1 Λ Λ 1 q

L L 丄 U U 丄 4 4 υ

0 0 1 Λ Λ 1 A c 1

L 0 丄 U U 丄 4 0 丄 π

1 1 7 1 Λ

L b 丄 U U 丄 4 1 丄 U Ό

0 1

0 丄 U U 1 4 8 1

丄 U

Q 1

4 0 丄 U U 1 5 2 1 A

丄 u

8 5 9 0 1 6 7 1 0 0

9 3 1 0 0 1 9 9 9 6

9 4 1 0 0 2 0 1 1 0 0

9 6 1 0 0 2 4 0 1 0 0

9 7 1 0 0 2 4 1 9 3

1 0 4 1 0 0 2 4 4 9 2

1 0 5 1 0 0 2 5 9 9 6

1 0 7 1 0 0 2 6 0 1 0 0

1 1 2 1 0 0 2 7 6 1 0 0

1 1 3 1 0 0 2 7 7 1 0 0

1 1 4 1 0 0

1 1 9 9 8 Control compound A 40

1 2 8 1 0 0 B 1

1 3 0 1 0 0 Control compound A Control compound B 'Pr

Claims

The scope of the claims

1. General formula [I]

[Wherein Q is ^N- ° or

-,,

X is a halogen atom, C, - ₃ alkyl group, C, - ₃ alkoxy groups, C, - ₃ alkyl Chiomoto, nitro group, C -! ₃ alkyl optionally substituted with a group amino group, or a C A -3 haloalkyl group;

r, and r 2 each independently represent a hydrogen atom, a C, _-3 alkyl group, a hydroxy group, a halogen atom, a thiocarbamoyl group which may be substituted with d- ₃ alkyl, or a C 1-3 alkyl. are unprotected Chio carbamoyl O alkoxy group, C, - ₃ alkoxides aryloxycarbonyl O alkoxy group, - ₃ alkoxy group, -S (0) "r 3 ( wherein n represents an integer of 0 ~ 2, r ₃ represents a C, _-3 alkyl group), an amino group optionally substituted with ₃ alkyl, or a C! _-3 alkylcarbonyloxy group or r! Sr 2 together An oxo group, a hydroxyamino group, a dsalkoxyamino group, or a methylene group;

_{_{, Y 2, Y 3, Y}} 4 and Υ respectively ₅ is a hydrogen atom, de alkyl group, C ₁₀ alkoxy groups, C, - ₆ alkylthio group, a halogen atom, § Mi be substituted by d-3-alkyl A hydroxyl group or a hydroxyl group;

However, when Y ₂ or Upsilon ₄ is not t- butyl group, Y ₃ is t one-butyl group, neo-pentyl group, t one butoxy group or t one Puchiruchio group, shows the t- Puchiruami cyano group. ] The compound represented by these.

2. —General formula [II] or [I] (II)

[11 ']

_{Wherein, X, Y,, Y 2} , Y 3, Y 4, Y 5, r, and r ₂ are as defined above. A compound represented by the general formula (I):

Wherein, Q, X, Y,, Y 2, Y 3, Y 4, Y 5, r, and r ₂ have the same meaning as above. ] The manufacturing method of the compound represented by these.

3. General formula [I]

[, Q, X, Y, _{_{wherein, Υ 2, Υ 3, Υ}} 4, Υ 5, and r ₂ have the same meaning as above. ] An insecticidal or acaricide comprising one or more of the compounds represented by the formula (1) as an active ingredient.