JPS5852202A - Insecticidal and acaricidal composition - Google Patents

Abstract

NEW MATERIAL:A 2-arylethyl ether or thioether derivative of formulaI(Ar is aryl; R1 is H, methyl or ethyl; R2 is 1-6C alkyl; R3 and R4 are H, halogen, lower alkyl or lower alkoxyl; X is O or S). EXAMPLE:3-(4-Fluorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether. USE:Useful as an insecticide and acaricide, and capable of extending the insecticidal spectrum by mixing and applying with an organic organophosphorus insecticide and acaricide and enhancing the insecticidal activity synergistically. PROCESS:A compound of formula II is reacted with a compound of formula III (either one of A and B is halogen; the other is X-M or both are hydroxyl; M is H, etc.) to give the compound of formulaI.

Description

Detailed Description of the Invention 2 [In the formula, Ar represents an aryl group, R. represents a hydrogen atom, a methyl group or an ethyl group, R2 represents a straight chain or branched alkyl group having 1 to 6 carbon atoms, R3 represents a hydrogen atom, a nitrogen atom, a lower alkyl group or a lower alkokino group, R4 represents hydrogen Atom, . . . represents a rogen atom, a lower alkyl group, or a lower alkoxy group, respectively.

X represents an oxygen atom or a sulfur atom. ] An insecticidal and acaricidal composition comprising one or more 2-arylethyl ether derivatives or thioether derivatives and one or more of the following acaricides: It is related to '.

Representative examples of the acaricides used in the present invention include the compounds shown below.

The numbers in parentheses indicate common names.

1.1-bis(p-chlorophenyl) -2,2,2-
Trichloroethanol (Kelsen), Ethyl 4,4'-dichlorobenzylate (Akar)bis(p-chlorophenoxy)methane (Neosarapyran), p-chlorophenyl p-chlorobenzenesulfonate
(Saraviran) Bis(p-chlorophenyl)methylcarbinol (DM
C) 2.4,5.4'-tetrachlorodiphenylsulfono (
Tetrachloro) 4-chlorophenyl 2.4.5-t! J Chlorophenyl azo sulfide (CPA8) Hx(4-chlorophenyl) disulfide (DDD8) 2,4-dinitro-0-cyclohexylphenol (
DN) 0,0-diethyl s-[(p-chlorophenylthio)
Methyl]phosphorodithioate (trithion) 0.0-
Diethyl 5-((2,5-dichlorophenylthio)methyl)phosphorodithioate (CMP) 2-5eC-butyl-4,6-dinitrophenyl-3methylcrotonate (vinapacryl)quinoxarif-2,3-diyl trithio Carbonate (Elasiton) 6-Methylquinoxaline 2,3-dithiocarbonate
(morestan) 2.3-dioxanedithiol S, 3-bis(0,0
-diethyl phosphorodithioate) (Dernac) monofluoroacetate, doo-p-dibromoanilide (Yanomite) N~methyl゛-N-(1-naphthyl) monofluoroacetamide (ethanol) N-methylbis(2,4- Quinryliminomethyl)amine (amitraz) (Osazana) Various insecticides and acaricides have been developed for agriculture, horticulture, and epidemic prevention, and carbamate and organophosphorus agents are mainly used for agriculture and horticulture. For epidemic prevention, pyrethroid and organophosphate drugs have been mainly used.

However, although some of these insecticides and acaricides have excellent properties such as fast-acting, systemic migration, and gas effect, they are not completely satisfactory in terms of insecticidal spectrum, residual effectiveness, toxicity to fish, and toxicity to humans and animals. It's not something I can do. Furthermore, as a result of the long-term use of these insecticides, pests that exhibit strong resistance to these insecticides have appeared in various places.

Paddy rice pests such as planthoppers and leafhoppers, vegetable pests such as the diamondback moth, sanitary pests such as houseflies, and mites that damage various crops have developed a remarkable degree of drug resistance. Organic/carbamate insecticides and carbamate insecticides are losing their practicality.

Furthermore, the use of large amounts of these chemicals in fields causes environmental pollution of soil, rivers, and other areas, and there is a strong desire for control using low dosages.

The novel compound represented by the above general formula [1] of the present invention is:
Although these compounds satisfy these requirements and have insecticidal and acaricidal activity even when used alone, the present inventors have further developed various compounds to achieve excellent control effects and reduce the amount of use of these compounds in actual situations. As a result of repeated research, it has been found that by applying a compound represented by the general formula [D] in combination with one or more organophosphorus insecticides and acaricides, the insecticidal effect is greater than when applied alone. They found that the spectrum was broadened and the insecticidal activity was synergistically enhanced, and they completed the present invention.

Representative examples of the compounds included in the general formula [I] of the present invention are shown in Table 1 below along with their physical properties.

The compound represented by general formula [I] is a new compound,
An example of its synthesis is shown below.

The compound represented by the general formula [1] is represented by the general formula [formerly R].

■ Ar-C-CH2-A [Former 2] The compound represented by the general formula [111] [In these formulas, Ar, R1, R2, R3, and R4 each represent the above-mentioned meanings, and the group "A" and the group B One of the groups represents a halogen atom and the other group represents an X-M group (in this formula, X represents the above meaning and M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom) or both represent a hydroxyl group].

Next, typical examples of the compounds of the present invention obtained in this manner are shown, but of course the compounds of the present invention are not limited to these examples.

In addition, in the general formula [1], the compound of the present invention has R9
When R1 and R1 are different groups, they have asymmetric carbon atoms and optical isomers exist, and these optical isomers and mixtures of these components are included.

3-(4-fluorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-
Fluorobenzyl 2-phenyl-2-methylpropyl ether and thioether, 3-phenoxy-4-chlorobenzyl 2-(4-chlorophenyl-2-1f-propyl ether and thioether, 3-phenoxy7-
4-fluorobenzyl 2-(4-methoxyphenyl)-2-methylpropyl ether and thioether,
3-phenoxy-4-fluorobenzyl 2-(3,4
-dimethylphenyl)-2-methy/l/7'pyl ether and thioether, 3-(4-fluorophenoxy)-4-fluorobenzyl 2-(4-methoxyphenyl)-2-methylpropyl ether and Thioether, 3-phenoxy-4-fluorobenzyl 2-
(4-Chlorophenyl)-2-ethylbutyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-butyl ether and thioether, 3-phenoxy-6-chlorobenzyl 2-(4-chlorophenyl) -2-Methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-3-methylbutyl ether and thioether, 3-(4-fluorophenoxy)-4-fluorobenzyl 2-(3
,4-dichlorophenyl)-2-methylbutyl ether and thioether, 3-phenoxy-5-methoxybe/zyl 2-'(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-(3-chlorophenoxy)-4- Fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and Hthioether, 3-(3-chlorophenoxy)-4-fluorobenzyl 2-(3,4-dimethyl)-2,3-dimethylbutyl ether and Thioether, 3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thionyte/
L, ,3-(2-fluorophenoxy)-4-fluorobenzyl 2-(3-chloro-4-chlorophenoxy)-2-methylpropyl ether and thioether, 3-(2-fluorophenoxy)-4- Fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoxy)-4-chlorobenzyl 2-(3,4-dimethoxyphenyl)-2-butylpropyl ether and t, -r, -fl, 3-phenoxy-4-fluorobenzyl 2-(naphthalen-2-yl)-2-methylpropyl ether and thioether, 3-phenoxy-
4-fluorobenzyl 2-C4-) toxicity 3.5-
dimethylphenyl) 2-)propyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-tert-butylphenyl)-2-
Methyl propyl ether and thioether, 3-, (
4-methoxyphenoxy)-4-fluorobenzyl 2
-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(3,4-dichlorophenyl)=2-methylpropyl ether and thioether,: 3-(4
-bromophenoxy)-4-fluorobenzyl 2-(
4-chlorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-inopropenyl)-butyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(3-trifluoromethyl phenyl)-2-methyl ether and thioether, 3-7 enoxy 4
-fluorobenzyl 2- (4-bromophenyl)-
2-methylpropyl ether and thioether, 3-
Phenoxy-4-methylbenzyl 2-(,l-chlorophenyl)-2-propyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-
Acetoxyphenyl)-2-methylbutyl ether and thioether, 3-phenoxy-4-fluorobairzyl 2-(3-methylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-5-fluorobenzyl 2-(3, 4-diethylphenyl)-
2-methylpropyl ether and thioether, 3-
7 enoxy 4-fluorobenzyl 2-(1,2,3
,4-tetrahydro)su7thalen-7-yl-2-methyl7°ropylether and thioether, 3-phenoxy-4-fluorobenzyl 2-(indan-5-yl)=2-methylpropyl ether and thioether, 3-( 3-fluorophenoxy) -4-fluorobenzyl 2-(3-methoxy-4-methylphenyl)-
2-methylpropyl ether and thioether, 3-
Phenoxy-4-fluorobenzyl 2-(3-ethoxy-4-bromophenyl)-2-methylpropyl ether and hiteoether, 3-phenoquine-4-fluorope/sil 27, (4-chlorophenyl)-2-methylbutyl ether and thioether, 3-7 enoxy 4
-fluorobenzyl 2-(3,4-(difluoromethylenedioxy)-phenyl]-2-methylglobyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2,3,3
-1-limethylbutyl ether and thioether, 3-
Phenoquine-4-fluorobenzyl 2-(4-difluoromethoquine 7-enyl) -2-methylpropyl ether oyohithioether, 3-(3-methylphenoxy-7)-4-fluorobenzyl 2-(4-chlorophenyl) -2-methylpropyl ether and thioether, 3-(3-chlorophenoxy)-5-fluorobenzyl 2-(3-nitro-4,5-dimethylphenyl)-2-methylpropyl ether and thioether,
3-(2-fluorophenoxy)-4-fluorobenzyl 2-(4-methylthiophenyl)-2-methylpropyl ether and thioether, 3-(3-fluorophenoxy)-5-fluorobenzyl 2-(3-chloro- 4-methquinphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-6-promopenzyl 2-(4-methylphenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoki7)-4 -fluorobenzyl 2-(3,4
-dichlorophenyl)-2-methylpropyl ether and thioether, 3-(4-methylphenoxy)-5
-fluorobenzyl 2-(4-methylsulfoquinphenyl)-2-methylglobyl ether and thioether, 3-phenoxy-2-fluorobenzyl 2-phenyl-2-methylpropyl ether and thioether,
3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2,1-dimethylbutyl ether and thioether, 3-phenoxy-6-bromobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3 - (4-fluorophenoxy)-2-fluorobenzyl 2-phenyl-2
-Methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-methylthiophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2
- <4-methylphenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoxy)-5-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4 -fluorobenzyl 2-(4-
Fluorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-5-fluorobenzyl 2-(4-10lophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-2-fluorobenzyl 2-(4- IJ methylphenyl)-2-
Methylpropyl ether and thioether, 3-phenoquine/-4-fluorobenzyl 2-(4-nitrophenyl)-2-methylpropyl ether and thioether, 3-phenoquine-5-chloropencyl 2-(4-chlorophenyl)-2- Methylpropyl ether and thioether, 3-phenoxy-6-chlorobenzyl 2
- (4-methylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-6-fluorobencyl 2-(4-methylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-
4-fluorobenzyl 2-(3,4-methylenedioxyphenyl)-2-methylpropyl ether and thioether, 3-(3-chlorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-butyl ether and thioether 3-phenoxybenzyl 2-(4-methylphenyl)-
2-methylpropyl ether, 3-phenoxybenzyl 2-(4-bromophenyl)-
2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-chloro-4-methylphenyl)-2-methylpropyl ether 3-phenoxybenzyl 2-(3.4-dibromonoenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(
4-chlorophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-tert-butylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-fluorophenyl)-2-methylpropyl ether 3-phenoxybenzyl 2- (3-bromo-4-chlorophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-dichlorophenyl) -
2-Methylpropyl ether, 3-phenoxybenzyl 2-(4-bromophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-ethylphenyl)-
2-methylpropyl ether, 3-phenoxybenzyl 2-(4-fluorophenyl)-
2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-chloro-4-fluorophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-ethylpheny3-phenoxybenzyl 2-(3,4- dichlorophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(
4-chloro-3-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-ter
t-butylphenyl)-2-ethylpropyl ether,
3-phenoxy/benzyl 2-(3,4-dimethylphenyl)-2-ethylpropyl ether, 3-phenoxy7
Benzyl 2-(3-10rho4~methylphenyl)-2
-ethylpropyl ether, 3-phenoquinbenzyl 2
-(3-bromo-4-chlorophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,4
-dibromophenyl)-2-ethylpropyl ether,
3-phenoxybenzyl 2-(4-chloro-3-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-10 lophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3 , 4-dimethylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-chloro-4-70lophenyl)-2 -Methylpropyl ether, 3-phenoxybenzyl 2-(3,4-dichlorophenyl)-2-
Methylpropyl ether, 3-phenoxybenzyl 2-
(3,4-dichlorophenyl)-2-ethylpropyl ether 3-phenoxybenzyl 2-(3-bromo 4-
fluorophenyl)-2-methylpropyl ether, 3-
Phenoxybenzyl 2-(3-bromo-4-70lophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-fluoro-4-bromophenyl)-2
-Methylpropyl ether, 3-phenoquinbenzyl 2
-(3-70rho-4-bromophenyl)-2-ethylpropyl ether 3-phenoxy/benzyl 2-(4-bromo-3-chloro-phenyl)-2-methylrefrobyl ether, 3-phenoxybenzyl 2-( 4-bromo 3-chloro-phenyl)-2-ethylpropyl ether 3-phenoxybenzyl 2-(4-fluoro-3-methylphenyl)-2-,7' thylpropyl ether 3-phenoxybenzyl 2-(4- Fluoro-3-methylphenyl)-2
-ethylproyl ether 3-phenoxybenzyl 2
- (3-fluoro-4-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2 - (
3-Fluoro-4-methylphenyl)-2-ethylpropylene ether, 3-phenoxybenzyl 2-(3-bromo-4-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3-bromo4) -methylphenyl)-2-ethylpropyl ether 3-phenoxybenzyl 2-(3.4-diethyl-phenyl)-
2-methylpropyl ether, 3-phenoxybenzyl 2-(3.4-diethyl-phenyl)-2-ethylpropyl ether 3-phenoxybenzyl 2-(4-isopropylphenyl) to 2-methylpropyl ether,
3-phenoxybenzyl 2-(4-inglobylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-diisopropylphenyl)-2
-Methylpropyl ether, 3-phenoxybenzyl 2-(3,4-diynepropylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,
4-Di-Tasha IJ-7” tylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,4-di-tarnia-butylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-( 3-ethyl-4-methylphenyl)-2-#fluprobyl ether, 3-phenoxybenzyl 2-(3-ethyl-4-methylphenyl)
-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-ethyl-3-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2- (
4-ethyl-3-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-tert-butyl-3-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2- (4- Tanyaly-phthyl-3-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-ingrovir-3
-Methyl-phenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-ingrovir=3-
) f-ruphenyl)-2-ethylpropyl ether, and the like.

Next, the method for producing the compound represented by the general formula [1] of the present invention will be described in more detail with reference to synthesis examples.

Synthesis Example 1 3-(4-bromophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether dry acetonitrile 20 ml! Sodium hydride (
60% in oil) 0.9 t, then 2-
(4-chlorophenyl)-2-methylpropyl alcohol-
2.8 t/10-ml acetonitrile solution at 50
It was added dropwise at ℃.

After heating under reflux for 30 minutes, 3-(4-bromophenoxy)-4-fluorobenzyl bromide 6.6t/10
m1 acetonitrile solution was added dropwise over 10 minutes, and
The mixture was heated under reflux for 1 hour. After cooling to room temperature, it was poured into water and extracted with toluene. The toluene extract was washed with saturated saline and dried with Glauber's salt. The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography on silica gel 1502 (developing solvent: toluene/n-hexane 1:l) to obtain the desired ether 461 (theoretical yield 65%). I got it.

nDl, 5806 shi”m 1590.1490,1435.+295.1
225゜naX +105.1020.830 bias -1 δCC/41.2.9 (8,6l-1), 3.32
(8.2 yen, 4.32 (S, 2H).

6.7-7.5 (m, ttH) Analysis result C23I42. Br CI FO2 Calculated value (%) C59,56H4,56Br 17
．． 23CI! 7.65 F 4.10 Actual value (@C59,85H4,64Br 17.
0 IC/ 7.77 F 4.00 Synthesis Example 2 3-Phenoxy-4-fluorobenzyl 2-(4-methylphenyl)-2-methylpropyl etherToluene 20 ml was added with sodium hydride (60
0.639 was heated to reflux, and 2-(
A solution of 710 ml of 4-)f-ruphenyl)-2-methylpropyl alcohol 1.797' 25% DMF-) was added dropwise over 15 minutes. After continuing stirring for 310 minutes, 710 ml of 3-phenoxy-4-fluorobenzyl chloride (3.0 t/)
It was dropped in 0 minutes. After further heating under reflux for 15 hours, the mixture was cooled to room temperature and drained into water.

After extracting with toluene and washing the toluene extract with water,
Dried with Glauber's salt. The crude ether obtained by distilling toluene off under reduced pressure was subjected to silica gel column 1 oor O column chromatography (developing solvent: toluene/n-hexane 1:
1) The desired pure ether 2.7F (theoretical yield 71%) was obtained by purification.

n is also 01.5611 i1m νmax 1600, 1500, 1435, 1290
, 1225°1105, 825. 695 bias-1 δCC/41.30 (8,j Seed2.27 (8,3H
), 3.34 (S, 2H).

4.34 (S, 2H), 6.8-7.4 (m,
12H) Analysis result C24R25FO';r Calculated value (%j C79,09H6,91F 5.21
Actual value (@ C79,23H7,01F 5.42 Synthesis Example 3 3-phenoxy-4-fluorobenzyl 2-(4-1
0 Lofenyl)-2-methylglovire 50% Na O
H aqueous solution 20? , 2-(4-ri o.

yx=le,)-2-melprovira/l/ko-/l
/ 5. C2,3-7 enoxy 4-fluorobenzyl bromide 862, and tetrabutylammonium 70 mite 1.1? The mixture was heated and stirred at 80"C for 1 hour. After cooling to room temperature, water was added, extracted with toluene, and washed with water. After drying the toluene extract with Glauber's salt, the toluene was distilled off under reduced pressure to obtain the obtained product. The resulting crude ether was purified by column chromatography on silica gel 2502 (developing solvent: toluene/n-hexane I:1) to obtain the desired ether 10.Or (theoretical yield: 80%).

n o' 1.5710 i1m νmax 1585.1490.1425.1280
．． 1210°1095, 1100. 820. 685
(m-'+5 CR41, 26 (S, 6H), 3.
30 (,S, 2H), 4.32 (,S, 2H)
.

6.8~7.4 (m, 12) (: Analysis result C23H2□C/FO2 Calculated value (see C71,77H5,76CI!9.21F
4.94 Actual value (@C71,95H5,55Ct 9.31F
5.02 Synthesis Example 4 3-phenoxy-4-fluorobenzyl 2-(3-methylphenyl)-2-methylpropyl ether toluene 207Wl! Concentrated sulfuric acid 2p, 3-phenoxy-
4-fluorobenzyl alcohol 2.7? , 2-(3-
Methylphenyl)-2-methylpropyl alcohol 21
The mixture was heated under reflux for 6 hours (the generated water was removed from the yarn using a water separator). After cooling to room temperature, water was added, and the toluene layer was separated, washed with water, and dried. The crude ether obtained by distilling toluene off under reduced pressure was
The product was purified by 0F column chromatography (developing solvent: toluene/n-hexane 1:1) to obtain the desired ether 192 (theoretical yield: 42%).

n o015582 1””’ 1600, 1505, 1435, 1290,
1225°ax 1'130. 710 bias δcc/4 l, 30 (S, 6 average, 2.29 (
S, 3.34 (S, , 2H).

4.33 (S, 2H), 6.8-7.4 (m,
12H) Analysis result C24H25FO□ Calculated value (inquiry) C79,09H6,91F 5.21 Actual value (@C79,31H7,02F s,ot Synthesis Example 5 3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl) -2-) Tylpropyl ether 4-chloroneophyl chloride 8.53f, 3-phenoxy-4-fluorobenzyl alcohol 8.72t,
45% NaOH3,9Y and dimethyl sulfoxide 4
B'f was heated and stirred at 140°C for 3 hours. 45% NaO
H1.8f was added, and the reaction was continued at the same temperature for an additional 4 hours. The reaction solution was discharged into 500 m of water, extracted with benzene, and the benzene extract was washed with water and then dried with Glauber's salt. The crude ether obtained by distilling off penzene under reduced pressure was separated and purified by column chromatography on silica gel 2501 (developing solvent: toluene/n-hexane 1:1) to obtain the desired ether 7.279 (theoretical yield 77). % vs consumption 4
-chlorneophyl chloride) was obtained.

〇 1.5710 The infrared spectrum and NMR spectrum were consistent with the ether obtained in Synthesis Example 3.

Synthesis Example 6 3-phenoxy-6-rioobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether 2-(4-chlorophenyl)-2-methylglobyl alcohol 20P13-phenoxy-6-rioropene 3.5f, 50% NaOH201, toluethylbenzylammonium bromide., 4fi50m,
Ya”57” to 75”□. The mixture was stirred at 1,50°C for 2 hours. After cooling to room temperature, water and benzene were added and stirred while cooling with ice water. After separation, the benzene layer was washed with water and dried with sodium sulfate. The crude ether obtained by distilling off benzene under reduced pressure was purified by column chromatography on silica gel 1502 (developing solvent: toluene-hexane) to obtain the desired ether 3.8f (87% of theoretical yield). Obtained.

n also”51.5854 111m νmax 1500.1480.1275.1260
．． 1215°1110.1020. 830(m"a"'< 1.29 (S, 6H), 3.44
(S, 2H), 4.49 (S, 2H).

6.7-7.5 (m, 12H) Synthesis Example 7 3-phenoxy-4-fluorobenzyl 2-(4-1
0 Lofenyl)-2,3-dimethylbutyl ether toluene 207 nl! Sodium hydride (60%
il) 0.60 f was added and heated to reflux, and to this
-(4-ri o o7
Stirring was continued for 10 minutes, and a solution of 35f of 3-phenoxy-4-fluoroperdyl bromide in 10 ml of toluene was added dropwise over 10 minutes. After further heating under reflux for 1 hour, the mixture was cooled to room temperature and drained into water. It was extracted with toluene, and the toluene extract was washed with water and then dried with Glauber's salt. The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography on 120 t of silica gel (developing solvent: toluene-hexane 1:1) to obtain the desired ether 2.8 f (
A yield of 72% of theory was obtained.

n I)"' 15656 1"1m1610,1530,1510,1450,1
300゜ax 1230, 1140.1120.103θSono-1δCC
'40.62 (d, 3H, J-6, 8H2),
0.85 (d, 3H, J -6,8Hz), 1
．． 19 (S, 3H), 1.9-2.3 (m,
IH) 4.30 (8,2H), 6.7-7.4
(m, 12H) The method for producing the starting material general formula (II) will be explained in detail below using synthesis examples.

Synthesis Example 8 It was synthesized according to the following order.

01 7! j-le 7se) 2) 'J-le 105'%KOH2
'Of.

Hz020 f/, ) 'J Ethylbenzylammonium bromide 22 was kept at 80°C to 90°C while methyl iodide (12 molar ratio to arylacetonitrile) was added dropwise over 1 to 2 hours. Then KOHl.

f,) IJ ethylbenzylammonium bromide 22
was added, and at the same temperature, a desired alkyl halide (12 molar ratio to arylacetonitrile) was added dropwise over 1 to 4 hours. After cooling to room temperature, it was extracted with toluene. The desired dialkyl form of arylacetonitrile was obtained from the toluene layer.

(The dialkyl form of arylacetonitrile synthesized in 21(1) was hydrolyzed with 50% H2SO4 or water-soluble diethylene glycol-KOH at 130 to 150°C.
Aryl-2-alkylgropion [18]

(R)+n R7mp HCH3-75~765℃ 3-CI CH3-66,5 to 675℃3.
4-Cl2CH3-93,5~945℃4-CH3C
H380~81.5℃ 4-CI C2H5-59~615℃4-O
CH3CH3-s 2.5-84°C (2-aryl-2-alkylpropionic acid synthesized in 31(2) was reduced with lithium aluminum hydride in tetrahydrofuran to obtain the desired 2-aryl-2-alkylpropyl alcohol. Profitable.

Synthesis Example 9 2-(4-chlorophenyl)-2-1f-propyl alcohol was synthesized according to the following sequence.

(1) Chlorobenzene 1692 and ferric chloride 1.5
After adding f, hydrochloric acid gas was blown in for 10 minutes. Then,
Tert-butyl chloride 462 was added dropwise at 30°C (1 hour) and kept at 30°C for an additional 2 hours. After washing with an aqueous sodium carbonate solution and water, distillation was performed under reduced pressure to obtain 4-tert-butylchlorobenzea 25S' (113°C/2
8M Bg) was obtained.

+21 4-tert-butylchlorobenzene 252 synthesized in (1), sulfuryl chloride 20? After adding a catalytic amount of benzoyl peroxide, the temperature was raised to 1
After keeping at 00℃ for 1 hour, it was distilled under reduced pressure and 2-(4
-chlorophenyl)-2-methyl-1-chloro-propane17. Of (121-123°C/10 Hg) was obtained.

(3) 27 t of magnesium (turnings) and a small amount of iodine as a catalyst were added to 100 m of dry tetrahydrofuran, and 2-(4-chlorophenyl) was added under heating under reflux.
-2-methyl-1-chloropropane 20.3r'i30
The mixture was added dropwise over a period of minutes, and heating and refluxing was continued for 10 hours. After cooling to room temperature, oxygen gas was blown in for 1 hour. Next, after adding a saturated aqueous ammonium chloride solution, most of the tetrahydrofuran was distilled off under reduced pressure, and the mixture was extracted with toluene. Toluene was distilled off under reduced pressure to obtain crude alcohol.

Then, recrystallization from cold hexane yielded the desired 2-(4-chlorophenyl)-2-methylglobyl alcohol 13.3
I got a 9.

m946~48℃ Analysis result Cl0H13C10 Calculated value (@C65,04H7,10CI 19.2
0 actual measurement value (fi C64, 18H6, 95CI 19
．． 16 Synthesis Example 10 2-(3,4-methylenedioxy/phenyl)-2=methylglobyl alcohol Synthesized according to the following sequence.

100ml of dry ether! Magnesium (turni)
ngs) 272, a small amount of iodine was added as a catalyst, and methyl iodide 171 was slowly added dropwise. Dripping end edge 3
Heating and refluxing was continued for 0 minutes. Then, 100 m/m of benzene was added dropwise while increasing the temperature to replace the ether with benzene.

While heating under reflux, raw material nitrile 1892 was added dropwise.

Further, after heating under reflux for 3 hours, 6N-i]cl was added under cooling.
! 20 me was added dropwise over 30 minutes. Then, the temperature was raised and the mixture was heated under reflux for 7 hours. After cooling to room temperature, the benzene layer was separated, washed with water, and dried with Glauber's salt. Benzene was distilled off under reduced pressure to obtain the desired 2-(,3,4-methylenedioquinphenyl)-
2-Methyl-3-butanone + 9.2 f was obtained.

(2) Bromine 128 was added dropwise to 741 n/ml of sodium hydroxide, 357 n/ml of water, and 10 m/ml of dioxane at 20°C or below.

Then, the temperature was raised to 90°C and 2-, (3,4-methylenedioxy7phenyl)-2-methyl-3-butanone lOf!
was slowly added dropwise, and the mixture was heated and stirred at 90 to 95°C for 2 hours.

After cooling to room temperature, add a specified amount of sodium bisulfite,
Extracted with toluene. The aqueous layer was acidified with concentrated hydrochloric acid and extracted with toluene. This toluene layer was washed with water, dried with Glauber's salt, and the toluene was distilled off under reduced pressure to obtain the desired 2-'
(3,4-methylenedioxyphenyl)-2-methyl-
Propionic acid 7.5r was obtained.

(3) The 2-(3,4-methylenedioxyphenyl)-2-methyl-propionic acid synthesized in (2) above was reduced with lithium aluminum hydride in tetrahydrofuran. -methylenedioxyphenyl)-2-methylglobyl alcohol was obtained.

ν Breath F 3390.1495.1235. t040c
m-'δCC' 1.25 (8,6H), 3.39 (
S, 2H), 5.87 (S, 2H).

6.6-6.9 (m, 3H) Synthesis Example 11 2-(4-difluoromethoxyphenyl)-2-methylbutyl alcohol Synthesized according to the following sequence.

(1) 2.4-bis(4-hydroxyphenyl)-4-
Methyl-2-pentene18. of 100 m 17 Setoni) After dissolving in IJ Le, 50% NaOH] Oj? was dripped. Then blowing of difluorochloromethane (Freon-22) was started at a temperature of 60-70°C. When about 60% of the required reaction amount was blown in (after about 20 minutes), the temperature was 50%.
%KOH10F was additionally charged and the blowing was continued.

Blowing was stopped when 15 times the amount of difluorochloromethane required for the reaction was blown into the reactor.

After cooling to room temperature, it was discharged into 500 ml of water and extracted with toluene. The toluene layer was washed with water, dried with Glauber's salt, and the toluene was distilled off under reduced pressure. The resulting crude ether was purified by silica gel 200fO column chromatography (developing solvent: toluene) to obtain the desired 2,4-bis. (4-difluoromethoxyphenyl)-4-methyl-2-pentene 192f was obtained. Yield: 77 cm.

n9°' 1.5285 (2) 2.4-bis(4-difluoromethoxyphenyl)-4-methyl-2-pentene 8.0 f facetoytoomI! KMri04' at 30℃
Added 30 tons. After stirring at 30° C. for 10 hours, 20 ml of ethyl alcohol was added dropwise under cooling to decompose excess KMnO4. After continuing to stir for 1 hour, the produced manganese dioxide was filtered and thoroughly washed with water and acetone. Acetone was distilled off under reduced pressure, a dilute aqueous hydrochloric acid solution was added, and the mixture was extracted with toluene. Rare N in toluene layer
a OH aqueous solution was added, shaken well, and then separated.

The resulting aqueous layer was made acidic with concentrated hydrochloric acid, extracted with toluene, washed with water, and dried.

Toluene was distilled off under reduced pressure to obtain 4.2f of the desired 2-(4-difluoromethoxyphenyl)-2-methylpropionic acid.

(mp, 68.5-69.5°C). Yield 84%.

δ"' 1.58 (S, 6H), 6.42 (
t, tH, J=75Hz)1 t76(broad
8.1l-1) ppm 1+3+ 2-(4-difluoromethoxyphenyl)-2- in a mixture of 20m of tetrahydrofuran and 0.5f of lithium aluminum hydride.
Methylpropionic acid2. ot/tetrahydrofuran 10
m/solution was added dropwise at 40°C. After dropping, raise the temperature 3
Refluxed for 0 minutes.

After cooling to room temperature, excess lithium aluminum hydride was decomposed by dropping ethanol, and water was further added to completely decompose it. The generated precipitate was removed by filtration, and tetrahydrofuran was distilled off under reduced pressure.

Extraction was performed with benzene, and the benzene layer was washed with water and then dried over anhydrous sodium sulfate.

Benzene was distilled off under reduced pressure to obtain the desired 2-(4-difluoromethoxyphenyl)-2-methylglobyl alcohol 1.
．． I got 8F. Yield 96%.

ν”1m3360.1510.1380.1220.1
185°ax 1130, 1040. 835 俤-1 Synthesis Example 12 2-(4-fluorophenyl)-2-methylbutyl alcohol Synthesized according to the following sequence.

(Li 4-fluorotoluene 1662, NH830,0
? , benzoyl peroxide 0.5 f, carbon tetrachloride 150 ml! was charged into a 300ml flask and refluxed for 20 hours. After cooling to room temperature, the precipitate formed was removed by filtration, and the CCt4 solution was washed with dilute alkali and water in that order, and dried with sodium sulfate. Carbon chloride was distilled off under reduced pressure to obtain crude 4-fluorobenzyl bromide 2882.

Mite 28.8f/ethanol 30ml solution 70~8
It was added dropwise at 0°C (30 minutes). The mixture was then kept at 80° C. for 50 hours, cooled to room temperature, and discharged into water.

Celite and benzene were added to this and stirred, and then Celite was removed by filtration. After separation, the benzene layer was washed with water and dried over anhydrous sodium sulfate. Benzene was distilled off under reduced pressure to obtain crude 4
-13.2y of fluorobenzyl cyanide was obtained.

V”m2270, 1615, 1520, 1430, 12
40゜ax 1170, 825 part-1 (crude 4-fluorobenzyl cyanide obtained in 21(1) 1282.50% NaOH 40t and triethylhensyl ammonium bromide 2v were placed in a flask and methyl iodide 142 was added dropwise with stirring. (70℃, 15
minutes).

After further holding at 70°C for 30 minutes, it was cooled to room temperature and discharged into ice water. Extraction was performed with benzene, and the benzene layer was washed with water and dried over Glauber's salt. Benzene was distilled off under reduced pressure, and α-methyl-4
-fluorobenzyl/anide 1347 was obtained.

d-methyl-4-fluorobenzyl/anide 707,
KOH1s? , H2O10v, triethylbenzylammonium bromide 2. O? The mixture was placed in a flask, and while stirring, ethyl 7°°'ide 0''' was added dropwise at 80'C for 11 hours.Then, the mixture was kept at the same temperature for 2 hours. The subsequent operations are as described above. 7.92 g of crude α-ethyl-α-methyl-4-fluorobenzyl cyanide was obtained.

Crude α-ethyl C1-Mef-4-fluorobenzyl cyanide 7.62, H2O2 oml! , concentrated sulfuric acid 20m
1 was placed in a flask and heated under reflux at 134 to 137°C for 55 hours. The mixture was cooled to room temperature and extracted with benzene. The benzene layer was extracted with dilute alkali, and the resulting dilute alkali layer was adjusted to pH 75 with concentrated hydrochloric acid, and extracted with benzene to remove impurities. Then, the aqueous layer was diluted with concentrated hydrochloric acid (I) H4,6 and extracted with benzene. The benzene layer was washed with water and dried with Glauber's salt. Benzene was distilled off under reduced pressure to obtain the desired 2-(4-fluorophenyl)-2-methylbutyric acid 3,81.

δcD” 0.85 (t, 3H, J=7Hz),
1.55 (S, 3H).

1.8-2.3 (m, 2H), 7. o ~7.
6 (m, 4H).

11.3 (broad F3. tH) (3) 20ml of tetrahydrofuran! , 2-(4-fluorophenyl) in a mixture of 0.52 lithium aluminum hydride
-2-Methylbutyric acid 30f! /tetrahydrofuran 107
nl! The solution was added dropwise at 40°C. After dropping, raise the temperature 3
Refluxed for 0 minutes. After cooling to room temperature, excess lithium aluminum hydride was decomposed by dropping ethanol, and water was further added to completely decompose it. The generated precipitate was removed by filtration, and tetrahydrofuran was distilled off under reduced pressure. Extraction was performed with benzene, and the benzene layer was washed with water and dried over Glauber's salt.

Benzene was distilled off under reduced pressure to obtain the desired 2-(4-fluorophenyl)-2-methylbutyl alcohol 267.

no31.5035 V"rr13360.1610, 1520, 1240,
1175°ax 1040, 840son-1 Synthesis Example 13 2-(4-Methylthiophenyl)-2-methylpropyl alcohol Synthesized according to the following sequence.

(1) Synthesis of 4-methylthiobenzyl chloride Methyral 1827 was dissolved in 7200 m/1,2-dichloroetha, and while cooling with water, anhydrous aluminum chloride 614
Added 2. Thioanisole 2482 was added dropwise to this at room temperature, and the mixture was stirred for 3 hours to carry out reaction A. After the reaction was completed, the mixture was poured into water, concentrated hydrochloric acid was added to dissolve the solids, and then extracted with benzene. The extract was washed with water, reconstituted aqueous sodium hydrogen oxide, and then water. After drying with Glauber's salt, the solvent was removed to obtain an oily residue with a weight of 30.79.

(2) Synthesis of (4-methylthiophenyl)-acetonitrile Dissolve soda cyanide 1057 in 121 of water and heat to 60"C. To this, add the oily substance 3072 obtained in (1) above dissolved in 35 ml of ethanol! It was added dropwise and refluxed for 4 hours to cause a reaction.It was worked up in the usual way and separated by column chromatography using benzene as a developing agent to obtain 147 (4-methylthiophenyl)-acetonitrile (oil). ) was obtained.

J"'4 2.37 (S, 3H), 3.56 (
Synthesis of 1,1-dimethylacetonitrile (4-methylthiophenyl)- Acetonitrile 13.1r to 13.9F
Obtained the objective.

δcc'4 1.66 (S, 6H), 2.45
(S, 3H), 7.2-7.6 (m, 4H) (4) Synthesis of 1-(4-methylthiophenyl)-1-methylpropionic acid Caustic potash 502, water 52, diethylene glycol 20
3.82 of 1-(4-methylthiophenyl)=11-dimethylacetonitrile was added to m/, cooled, drained into water, and extracted with benzene. When the aqueous layer was acidified with concentrated hydrochloric acid, a precipitate was formed. This was extracted with ether, washed with saturated saline, dried with a sieve, and the solvent was removed to form a solid 1-(
4-Methylthiophenyl)-1-methylpropionic acid So 192 was obtained.

δ""'d6 1.54 (S, 6H), 2.43
(S, 3H).

7.0-7.5 (m, 4H) (5) Synthesis of 2-(4-methylthiophenyl)-1-methylpropyl alcohol Reduction with lithium aluminum silhydride in a conventional manner.
-methylthiophenyl)-1-methylpropionic acid 1.
1.59 f of the target alcohol was obtained from 9y.

δ”'4 1.26 (S, 6H), 2.39 (
S, 3H), 3.38 (8, 2H), 7.0-7
．． 4 (rn, 4H) Synthesis Example 14 2-(4-chlorophenyl)-2-, +j chill 7'.

Synthesis of pyruthiol It was synthesized according to the following order.

Synthesis of (112-(4-chlorophenyl)-2-methylpropyl tosylate) Add 20 ml of pyridine to 10.89 ml of 2-(4-10 chlorophenyl)-2-methylpropyl alcohol and 10.89 p-)luenesulfonyl chloride, The mixture was drained into ice water, acidified with dilute hydrochloric acid, and drained. The benzene layer was washed with saturated brine, dried over Glauber's salt, and the solvent was distilled off under reduced pressure. 19. A white solid residue of -3f was obtained. Melting point 6
9~71.5℃a"'41.31 (S, 6H),
2.44 (S, 3H), 3.89 (S, 2H)
, 7.13 (S, 4H) , 76 to 7.18
0 [m, 4H (AB Type)] VKBr 1595.1480.1355.1175
．． 970゜ax 825 (m-1 (2) bis-(2-(4-chlorophenyl)-2methylpropyl) disulfide synthesis (1)) 13.0? and sodium hydrogen sulfide 20
．． 0f (70% product) and 90% ethanol 100ml
The mixture was reacted for 3 hours under reflux while stirring. The reaction product was discharged into water, extracted with benzene, and the benzene layer was washed with water and then dried with Glauber's salt. Benzene was distilled off under reduced pressure to obtain a liquid residue 7.9f.

This was separated by silica gel column chromatography using a mixed solvent of benzene-hexane (1:a) to obtain the target product 5.31i' (oil).

ν”m2950, 1500, 1410, 1395, 13
80゜aX 1120, 1105.1020.830.755ynδ
”'41.31 (8,6H), 2.81 (S,
2H), 7.18 (d, 4H) Elemental analysis CH8C/calculated value'/, 60.1? 6.01 16.06
17.76 measured value'/, 59,06 6.07 16.
55 17.56(3)2-(4-chlorophenyl)-
Synthesis of 2-methylglobylthiol25mI dry ether! Lithium aluminum hydride 0. O95f was suspended, and 1.02 mL of ether-dissolved sitahis-(2-(4-chlorophenyl)-2-methylpropyl) disulfide was added dropwise thereto, and the reaction was allowed to proceed under reflux for 2 hours. was poured into water, 15% diluted sulfuric acid was added, and extracted with benzene.The benzene layer was washed with saturated brine, dried over Glauber's salt, and the solvent was distilled off under reduced pressure to obtain a liquid residue of 1.02%. Ta.

ν”” 2965, 2570, 1495, 1405, 1
390゜aX 1370, 1105.1020.830m-"J"'4
0.80 (t, IH), 1.33 (S, 6H
).

2.68 (d, 2H), 7.23 (S, 4
H) Compounds listed in Table 1 above, other than the target compounds shown in this synthesis example, can also be synthesized according to the above synthesis examples.

The first feature of the insecticidal/acaricidal composition of the present invention is that
It has a broader insecticidal spectrum and synergistically enhanced insecticidal efficacy than when the compounds shown in the table are applied alone. That is, the composition of the present invention can be used for paddy rice, field crops,
Agriculture, horticulture, and forest pests that cause damage to cotton, fruit trees, forests, etc. (e.g., leafhoppers, planthoppers, grasshoppers, rice weevils, rice weevils, stink bugs, aphids, green caterpillars, armyworms, mealybugs, mealybugs, seed flies, sink beetles, scale insects,
A wide range of pests, including storage pests such as black weevils and snail moths, and sanitary pests such as flies, moths, cockroaches, etc.) On the other hand, it has a control effect at low concentrations.

The second feature of the composition of the present invention is that it is effective against insect pests that have already developed resistance to organophosphorus insecticides and acaricides and/or carbamate insecticides and acaricides. It is effective, and it is also difficult to develop chemical resistance against various insect pests.

The third feature of the composition of the present invention is that it has rapid action that is not found in general organophosphorus insecticides and acaricides and carbamate insecticides and acaricides, and can be used within a short period of time after spraying. In other words, it is possible to cause the pest to fall and turn upside down.

Furthermore, the fourth feature is that it has many excellent features such as low toxicity to fish and warm-blooded animals and no risk of causing environmental pollution, making it an extremely ideal insecticide and acaricide. That is what can be said.

When actually applying the composition of the present invention, it is effective enough to dilute the composition itself, but in order to make it easier to use as a pesticidal agent, various carriers are mixed into the formulation.
This product is generally diluted and applied as necessary. The formulation of the composition of the present invention does not require any special conditions, and can be formulated into emulsions, water concentrators,
Powders, fine granules, granules, oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.), fogging agents, etc.
It can be prepared in any form such as a non-thermal fumigant or a poisoned bait, and can be used for various purposes depending on the purpose.

The composition of the present invention has high stability against light, heat, oxidation, etc., but if necessary, antioxidants or ultraviolet absorbers, such as phenol derivatives such as BIT and BHA, bisphenol derivatives, phenyl β A composition with stable effects can also be obtained by adding an appropriate amount of amyl aminos or benzophenone compounds such as -naphthylamine, phenyl β-naphthylamine, and a condensate of phenetidine and acetone as a stabilizer.

In addition, for the purpose of obtaining a multipurpose agricultural chemical, the composition of the present invention may include an attractant, a repellent, a fungicide, a herbicide, a plant growth regulator,
It can also be used by adding fertilizer etc.

The composition ratio of the compound of general formula [I] and the acaricide in the composition of the present invention is 99:1 to 1:99, preferably 1:9 to 1
:1.

When the composition of the present invention is formulated, the concentration of the active ingredient is 5 to 50 h for emulsions, 0.3 to 3 h for powders, and 5 to 5 h for irrigation agents.
0%, and for granules, 05 to 50% (all percentages by weight) is desirable.

Next, some examples of formulations in which the composition of the present invention is used as an agrochemical or an epidemic prevention drug will be shown, but the present invention is not limited to these. All "parts" indicate "parts by weight."

The acaricides in the formulation examples refer to the compounds described herein.

Similarly, "compounds in Table 1" refers to any one of the compounds listed in Table 1.

Formulation Example-1 5 parts of the compound shown in Table 1, 20 parts of acaricide, 10 parts of emulsifier Tsurupol 5M-200 (Toho Chemical brand name), 6 parts of xylene
5 parts were stirred and mixed to form an emulsion.

Formulation Example-2 1 part of the compound shown in Table 1 and 5 parts of acaricide are dissolved in acetone, 94 parts of clay for powders are added, and the mixture is stirred to evaporate the acetone to obtain a powder.

Formulation Example-3 Add 25 parts of acaricide to 5 parts of the compound in Table 1, add 5 parts of the emulsifier Tsurupol 355TLL (trade name of Toho Chemical), stir well, and add 300 mesh of diatomaceous earth 6.
Add 5 parts and stir and mix thoroughly in a Raikai machine to prepare a wettable powder.

Add 10 parts of acaricide to 3 parts of the compounds in Table 1, and add 8 parts of clay.
3 parts and 4 parts of Toyolignin CT (trade name of Toho Chemical) were added, mixed well, water was further added, and after stirring and mixing, the mixture was granulated using a granulator and dried to form granules.

Formulation Example-5 Add 5 parts of acaricide to 1 part of the compound shown in Table 1, dissolve in white kerosene, etc., and make 100 parts of the total to obtain an oil solution.

Formulation Example-6 Compound 022 in Table 1 with 0.2 t of acaricide and 0.9 of K synergist? , BHTo3f was added and dissolved in 20ml of methanol, and each carrier for mosquito coils (tab powder, lees powder, wood flour
99.42 (mixed at a ratio of 5:1) and evaporated the methanol, add 150ml of water!
, knead thoroughly, mold and dry to make mosquito coils.

Formulation Example-7 Compound 0.1 in Table 1? , acaricide 011, synergist 1
Add BHTO:2r to 0f and dissolve in chloroform,
The fibers were adsorbed onto F paper with a thickness of 0.30 nm and heated on an electric heating plate to obtain a fiber fumigation composition.

Formulation Example-8 0.1 part of the compound in Table 1, 0.1 part of acaricide, 0 synergist
．． 3 parts of Kijirole, 7 parts of deodorized kerosene, and 75 parts of deodorized kerosene were mixed and dissolved. Fill this into an aerosol container and attach the pulp. Through the pulp part propellant (liquefied petroleum gas) 80
The part is processed and made into an aerosol.

Formulation Example-9 Compound 01 part in Table 1, 0.1 part acaricide, synergist 03
11.5 parts of deodorized kerosene, 1 part of emulsifier Atmos 300 (trade name registered by Atlas Chemical Co.), and 50 parts of pure water.
and emulsify. This is filled into an aerosol container with 3.7 parts of a 3:1 mixture of butane bromide and deodorized propane to form a water pace aerosol. .

Next, we will list specific insect pest groups to which the insecticide and acaricide of the present invention can be applied [scientific name (Japanese name)].

1. Hem1ptera (Hemiptera) Nephot
ettix cincticeps Uhler (
tsu? 8 partsgatella furcifera Horva
th (+ white planthopper) Nilaparvata l
ugens 8tal ()Laode
lphax 5triatellus Fallen
(Eurydema rugosa)
Motschulsky (nagame) Eysarcor
ia parvus Uhler () Halyomorpha m1sta Uhler (
Lagynotomus e, Ion
gatus Dallas (rice stink bug) Noza
ra viridula Linne (Southern green stink bug) C1etus trigonus Thunb
erg Stephanitis
nashi Bsaki et Takeya 8tephanitis pyrioides 5co
tt (77 Jigunbai) Psilla pyrisug
a FQrster (Psylla)
mali Schmidberger Aleurolobus taonabae K
uwana (grape whitefly) D%aleurodes cltr+, Ashmead
(Mandarin orange pear A i
A Rami) Trialeurodes vaporraiorum
Westwood Brevicoryne brassicae Lin
n5 (radish aphid) Myzus persicae 5ulzer (peach aphid) Rhopalosiphum mai
dis Fitch Icerya purchasi Maskell (
Planococcus citri R15so (
Unaspis yanonensis Kuwana
(Lepidoptera) 2. Lepidoptera (Lepidoptera) Cane
phora asiatica Staudinger
(Minoga) Spulerina astaurcta
Meyrick (Nasihonga) Lithocoll
etis ringoniella Matsumur
a (Plutella xylostella Linn)
e (diamond moth) Promalactis inopi
sema Butler (watamiga) Adoxop
hyes orana fischer von
Roslerstamm Bactra furfurana Haworth
(Igusa Shinmushiga) Legumi old vora gl
ycinivore! la Matsumura Cnaphalocrocis medinalis
0uenee (-y Punomeiga) Etiella zinckenella Treat
Ostrinia furnacalis Guene
e (7'7//l'iga) Pleuropty
a derogata Fabricius Hyphantria cunea Drur
y (American White Wife) Abraxas m1ra
nda Butler Lymantria dispar 'japonic
a Motschulsky' (Gypsy moth) Agrotis segetum Denis et
8chiffer m1iller (Kaburayaga) Helicoverpa armigera Hibn
er (Pseudaletia 5e)
parata Walker (7r7 YO)tsu)Ma
mestra brassicae Linne (
Plusia nigrisigna Wa
lker (p + naginuwaba) Spodopter
a l 1tura Fabl 1cius (Hasmore 1 tow) Parnara guttata Brem
er et Gray Pieris rapae cruci4ra Boi
Chilo 5uppressalis Walker
r (=cameiga) 3, Co1eoptera
(Coleoptera) Melanotus fortnumi C
andeze (ma/l/kubikushiko plating) Anthrenus verbasci Linn;
(Tenebroides mauritanicus)
Linn5 (Kokunust) Lyctus brun
neus 5tephens (Oyster wood beetle) 1
1enosepilachna vigintioc
Monochamus alternatus Hop
e (Pine/Pine beetle) Xylotrechus pyrrhoderuSBa
tes (grape beetle) Aulacophora femoralis Mot
schulsky (Oulema oryzae Kuwayama)
Phyllotreta 5tri
olata Fablicius Callosobruchus chinensis
Linne (Azuki weevil) EchinocnemlThs squameus B
Bllber (rice weevil) 8itophilus oryzae Linne (
:I:I whale) Apoderus erythrog
aster, Vollenhoven Rhynchites heroes Roelofs
(Momochokkiri weevil) Anomala cuprea Hope (Douganepuibui) Popil, J6 japonica N
ewmdn (-qmekogane)4. Hymenop
tera (Hymenoptera) Athalia rosae j
aponensis Rohwer (Cabrababachi) Arge 51mlis Vo eyes enhoven (
Rurichu l/7ji) Arge pagana Pan
zer 5, Dipter
a (Diptera) Tipula aino Alexander (-!
j - Culex pipiens f
atigans Wiedemann (Aedes ae?) ypti Linn5 (Aedes aegypti) Asphondylia sp, (Sybean pod fly) Hylemya antiqua Me
igen (p) Hylemya pl
atura Meigen (seed fly) Musca
domittica vicina Macqua
rt (Housefly) Dacus cucurbitae
Coqutllett Chloro
ps oryzae Matsumura (, (Nekara fly) Agromyza oryzae Munak
ata (rice leafminer fly) 6, 8iphonap
tera (Hymenoptera) Pulex 1rritans
Linne (human flea) Ctenocephalides canis Cur
tis (dog flea) 7, Thysanopte
ra (Hymenoptera) Scirtothrips dorsa
lis Hood (Tea thrips) Thrips tabaci Lindeman (
Chloethrips oryza
e Williams (rice thrips) 8 Ano
plura Pediculus hum
anus corporis De 0eer (Popular lice) Phthirus pubis Lin edition (Popular lice)
Haematopinus eurysternus
N1tzsh (Uzi 7 Rami) 9, Psocopte
ra (Trogtum pulsa)
terium Linne Li
poscelis bostrychophilus
Badonnel (Hiratachatate) - 10, 0rthhoptera (Orthoptera) Gryll
otalpa africana Pa1isot d
e Beauvois Locusta migratoria danica
Linn5 () / Samabatsuta) Oxya yezoensis 8hiraki (
Dictyoptera) 11, Dictyoptera
(Opiptera) Blattella germanica
Linn5 (German cockroach) Periplane
ta fuliginosa 5erville (Black cockroach) 12, Acarina (Acarina) Boophilus m1croplus Canes
trini (Polyphagotarsonemus Iatus)
Banks (Chano dust mite) Panonychus citri Mc Grego
r (citrus spider mite) Tetranychus ci
nnabarium Boisduval (,=-Semitic spider mite) Tetranychus urticae Koch
(Two-spotted spider mite) (Red mite) Next, the effects of the composition of the present invention as an insecticide and acaricide will be explained in detail by giving test examples.

Test Example: A leaf disk of a kidney bean leaf punched out with cork polar (diameter 15 m5) was placed on water-soaked absorbent cotton (2111*X21) II), and 10 adult two-spotted spider mites were released to spawn. Using a spray tower, spray 3 ml of each of the single and mixed 50 ppm emulsions of each test metal and drug prepared by the method in Formulation Example 1! Sprayed.

After the treatment, it was left in a constant temperature room at 25° C., and 24 hours after the treatment, live and dead insects were examined, and the adult killing rate was calculated. The adults were then removed, and the remaining eggs were treated again with the above three chemical solutions.

After the treatment, the eggs were left to stand in a constant temperature room at 25°C, and 7 days after the treatment, viable and dead eggs were examined to calculate the ovicidal rate. The results are shown in Table 2 below.

When the acaricide was used alone, the adult mite killing rate was low and the adult mites remained alive, but when the compounds shown in Table 1 were mixed, the adult mites could almost certainly be killed.

In addition, the ovicidal rate was low when using the compound in Table 1 alone, but by mixing it with an acaricide, the effect was radical, and the adulticidal rate and ovicidal rate increased by 2 to 10 times.

, the acaricides described herein other than Kelsen may also be used.
Table 15 0 10 0 16 5 21 15 29 40 30 30 39 0 41 0 42 5 44 0 48 0 51 5 54 0 58 0 63 0 72 10 78 30 7p 50 81 5 84 0 87 10 91 10 40 100 10 36
9340 100 7
36 7440 100 6
36 8740 100
13 36 10040
100 28 36 1004
0 100 37 36
10040 +00 43
36 10040 100
7 36 8340 90
0 36 8640
100 0 36 75
4 (110003688 40100143694 401002136100 40100936100 4010043696 409003672 40100, 03684 401004236100 401005136100 40100123696 4 01000368+

Claims (1)

[Scope of Claims] 2 [In the formula, Ar is an aryl group, R1 is a hydrogen atom, a methyl group or an ethyl group, and R2 is a straight chain or branched alkyl group having 1 or more carbon atoms], R3 is hydrogen R4 represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, respectively. X represents an oxygen atom or a sulfur atom. An insecticidal and acaricidal composition comprising one or more 2-arylethyl ether or thioether derivatives represented by the following formula and one or more acaricides.