JPS5849303A - Insecticidal and miticidal composition - Google Patents

Abstract

PURPOSE:To provide the titled composition containing a 2-arylethyl(thio)ether derivative (novel compound) and an agent causing abnormal metamorphosis to arthropods, e.g. juvenile hormone activating substance, etc., and capable of completely controlling the insects and mites at low dose compared with the separate use of each component. CONSTITUTION:The objective composition is prepared by mixing (A) a novel 2-arylethyl ether or thioether derivative of formula (Ar is aryl; R1 is H, CH3 or C2H5; R2 is 1-6C alkyl; R3 and R4 are H, halogen, lower alkyl or lower alkoxy; X is O or S), e.g. 3-(4-bromophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)- 2-methylpropyl ether with (B) an agent such as chitin synthesis inhibiting agent, anti-juvenile hormone activating substance, etc., at a ratio of preferably (1-9):1. The mixture has broad insecticidal spectrum and synergistically increased insecticidal activity, and exhibits rapid activity, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel compounds of the following general formula [wherein Ar
is an aryl group, R□ is a hydrogen atom, methyl group or ethyl group, R2 is a straight chain or branched alkyl group having 1 to 6 carbon atoms, R3 is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group wo and R4 each represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group. X represents an oxygen atom or a sulfur atom.

] containing one or more 2-arylethyl ether derivatives or thioether derivatives, and one or more chitin synthesis inhibitors, juvenile hormone active substances, and anti-juvenile hormone active substances. This invention relates to an insecticidal/acaricidal composition.

A drug that causes abnormal metamorphosis in arthropods used in the present invention,
That is, the following five types of compounds are currently known as chitin synthesis inhibitors and juvenile and antijuvenile hormone active substances. Values within 0 indicate common names.

Benzoyl urea compounds represented by 1-(4-chlorophenyl)-5-(2,6-difluorobendiyl)urea (PH6040), 6-7di)"-N-cyclopropyl-N'-ethyl -1
,3,5-)riazine-2,4-diamine (CGA-1
9255), triazine compounds represented by 1-(4
'-ethylphenoxy)-6,7-epoxy-6,7-
Dimethyl-2octanone, (R-2o4ssj, isopropyl (2E14E)-11-methoxy?-3°7.1
Juvenile hormone analogues represented by 1-1-dimethyl-2,4-dodecadienoate (aldocyto), 6,'7-dimethoxy-2-dimethylchromene ()゛Recosen■) Representative chromene compounds.

Conventionally, organic phosphorus compounds and carbamate compounds have been used as insecticides and acaricides for agriculture and horticulture and insecticides for epidemic prevention. Although some of these insecticides and acaricides have excellent features such as systemic transferability and gas effect, they are not all satisfactory in terms of insecticidal spectrum, residual effectiveness, fish toxicity, human and animal toxicity, etc. Furthermore, as a result of the long-term use of these chemicals, pests that are highly resistant to these chemicals have appeared in various places.

Planthoppers and leafhoppers that are rice pests, diamondback moths that are vegetable pests, house flies that are sanitary pests, and spider mites that damage various crops are particularly susceptible to drug resistance. Compounds are losing their practicality. Furthermore, the introduction of large amounts of these chemicals into fields causes environmental pollution in soil, rivers, etc.
Infection is also a problem, and there is a strong desire for control at low levels.

The novel compound represented by the 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 conducted various studies to obtain high pesticidal effects and reduce the amount of use of these compounds in practical situations. As a result, a mixture of the compound represented by the general formula [I] and one or more substances that cause abnormal metamorphosis, such as a chitin synthesis inhibitor, a juvenile hormone active substance, and an anti-juvenile hormone active substance, has been developed. The present invention was completed based on the discovery that the amount of medication needed to completely control insects and mites can be lowered compared to when these compounds or substances are applied alone.

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

The compound represented by the general formula (1) is a new compound, and an example of its synthesis is as follows. General formula [
1] The compound represented by the general formula CHI) R] ♂ Ar-c -CH2-A (1)2 The compound represented by the general formula CI) 3 [In these formulas, A', R□, R2, R3 , R4 respectively represent the above meanings, one of the groups A and B represents a ) rogen atom, and the other group represents an X-M group (in this formula, X represents the above meaning, and M represents It can be obtained by reacting with a compound represented by a hydrogen atom, an alkali metal atom, or a compound in which both alkali groups represent hydroxyl groups.

Next, do it like this! Typical examples of the compounds of the present invention that can be used are shown below, but the compounds of the present invention are of course not limited to these examples.

In addition, in the general formula [1], the compound of the present invention includes R,
and R2 are different groups, which have asymmetric carbon atoms and have optical isomers, and include mixtures of these optical isomers and these components.

3-(4-fluorophenoquine)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 6-phenoxy-4-fluorobenzyl 2-phenyl-2-)propyl ether and Thioether, 3-phenoquine-4-chlorobenzyl 2-(4-10 phenyl-2-methylpropyl ether and thionidel, 3-phenoxy-
4-fluorobenzyl 2-(4-methoxyphenyl)
-2-methylpropyl ether and thioether, 6
-phenoxy-4-fluoropennlu 2-(5.4-
cy'tylphenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoxy)-
4-fluorobenzyl 2-(4-methoxyphenyl)
-2-methylpropyl ether and thioether, 6
-Phenoxy-4-fluorobenzyl 2=(4-chlorophenyl)-2-ethylbutyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-
(4-chlorophenyl)-butyl ether and thioether, 6-phenoxy-6-chlorobenzyl 2-(
4-10 chlorophenyl)-2-methylpropyl ether and thioether, 6-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-3-methylbutyl ether, olophenoxy)-4-fluorobenzyl 2-(3
, 4-dichlorophenyl)-2-methylbutyl ether and thioether, 3-fe/ki'/-5-methoxybenzyl 2-(4-chlorophenyl)-2-methylglobyl ether, 3-(3-chlorophenol) -4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 5-(s-chlorophenoxy)-4-fluorobenzyl 2-(ro,4-dimethyl) -2,3- Dimethylbutyl ether and thioether, ro-phenoxy/-4-fluorobenzyl 2-'(4-1' lorophenyl)-2-methylpropyl ether and thioether, 3-(2-fluorophenoxy)-4-fluorobenzyl 2-(3 -chloro-4-chlorophenoxy)
-2-methylpropyl ether and thioether, 6
-(2-fluorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoxy14-chlorobenzyl 2- (3゜4-dimethoxyphenyl)- 2-butylpropyl ether and thioether, di-phenoquine-4-fluorobenzyl 2-
(Naphthalen-2-yl)-2-methylpropyl ether and thioether, ro-phenoxy-4-fluorobenzyl, 2-(4-methoxy-3,5-dimethylphenyl) 2-methylpropyl ether and thioether, 3-phenoxy- 4-fluorobenzyl 2- (
4-tert-butylphenyl)-2-methylpropyl ether, 3-(4-methoxyphenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylglobyl ether, 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-ia7'ropenyl)-butyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2- (5
-) IJ fluoromethylphenyl)-2-methyl ether oyohithioether, 3-phenoxy-4-fluorobenzyl 2-(4-bromophenyl)-2-methylglobyl ether oyohithioether/l/, 3-phenoxy =4-methylbenzyl 2-(4-chlorophenyl)-2-7”ropylether, 6-
Phenoxy-4-fluorobenzyl 2-(-4-acetoxyphenyl)-2-methylbutyl ether and thioether, 6-phenoxy-4-fluorobenzyl 2
-(j-methylphether)-2-methylpropyl ether and thioether, 3-phenoxy-5-fluorobenzyl 2-(3,4-dimethylphenyl)-2-methylpropyl ether and thioether, 6-phenoxy'/-4- Fluorobenzyl 2-(1,2,s,s
-tetrahydro)naphthalen-7-yl-2-methylpropyl ether and thioether,
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 hythioether, 6-phenoxy-4-fluorobenzyl 2-(4-1'rollophenyl)-2-methylbutyl ether and hythioether, 6-phenoxy-4-fluorobenzyl 2-(3,4-(difluoromethylenodioxy)-phenol)-2-methylglobyl ether and thioether, 6-phenoxy-4-fluorobenzyl 2-(4-riconvesylophenyl)-2,3, 3-t+)) Tylphthyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-difluoromethoxyphenyl)-2-methylpropyl ether and thioether, 5-(3-methylphenoxy)-4
-fluorobenzyl 2- (4-chlorophenyl)-
2-Methylglobyl ether oyohithioether, 3-
(5-chlorophenoxy)-5-fluorobenzyl 2
-(5-nitro-4,5-dimethylphenyl)-2-mer F-rubropylether 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, 6-phenoquine-6-promobenzyl 2-(4-methylphenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoxy)- 4-fluorobenzyl 2-(3,
4-dichlorophenyl)-2'-mefk 7' 0vyl ether and thioether, 3-(4-methylphenoxy)-5-fluorobenzyl 2-(4-methylsulfoxyphenyl)-2-methylpropyl ether and thioether, 6-7enoxy-2-fluorobenzyl 2-7enyl-2-methylpropyl ether and thioether, 6-phenoxy-4-fluorobenzyl 2
-(4-chlorophenyl) -2,3-dimethylbutyl ether and thioether, 6-phenoxy-6-promopenzyl 2-(4-10lophenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoxy)-2 -fluorobenzyl 2-phenyl-2-methyl 7'ct hyl 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, 5-phenoxy-4-fluorobenzyl 2-(4-fluorophenyl)-2-methylpropyl ether and thioether, 6-phenoxy-5-fluorobenzyl 2-(4-chlorophenyl )-2-methylpropyl ether, yohythioether, 6-phenoxy-2-fluorobenzyl 2- (4-) IJ methylphenyl)=2-methylbutyl ether and thioether, 6-phenoxy-4-fluorobenzyl 2-(4
~ Nitrophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-5-chlorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 6-phenoxy-6-chlorobenzyl 2-(・4 -methylphenyl)-2-methylpropyl ether and thioether, 6-phenoxy-6-fluorobenzyl 2-(4-methylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(3 ，
4-)fL/dioxyphenyl)-2-methylglobyl ethyl and thioether, 3-(3-chlorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-butyl ether, yohythioether 3-phenoxy7penzyl 2- (4-methylphenyl)-
2-Methylpropyl ether, 6-phenoxybenzyl 2-(4-bromophenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(3-chloro-4-
methylphenyl)-2-methylpropyl ether, 5-phenoxybenzyl 2-(3,4-dibromophenyl)-2-methylpropyl ether, 5-phenoxybenzyl 2.-(4-chlorophenyl)-2-ethylpropyl ether , 3-phenoxybenzyl 2-(4-t
ert-butylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-fluorophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3-bromo-4-chlorophenyl)-2-ethylpropyl Ether, 6-phenoxybenzyl 2-(3,4-dichlorophenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(4-bromophenyl)-2-methylpropyl ether, 6-phenoxybenzyl 2-(4- ethyl phenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2'-(a-fluorofe=/L/)
-2-Ethylpropyl ether, 3-phenoxybenzyl 2-(5-10ro-4-70lophenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(,4-1, tylphenyl)-2-ethylpropylether Pyl ether, 6-phenoxybenzyl 2-(3,4-dichlorophenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(4
-Chloro-3-methylphenyl)-2-methylpro-1
ether, 6-phenoxybenzyl 2-(4-tert-butylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-dimethylphenyl)-2-
Ethylpropyl ether, 3-phenoxybenzyl 2-
(5-chloro-4-methylphenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2- (5-7" como-4-chlorophenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(5, 4-dibromophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-chloro-3-methylphenyl) -2
-ethylpropyl ether, 3-phenoxybenzyl 2-(4-chlorophenyl)-
2-methylpropyl ether, 3-phenoxybenzyl 2- (3,-,4-dimethylphenyl)-2-
Ethylpropyl ether, 3-phenoxybenzyl 2-
(4-Methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(5-chloro-4-fluorophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-chlorophenyl) )-2-ethylpropyl ether, 6-phenoxybenzyl 27 (5,4-dichlorophenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(5
-bromo-4-70-phenyl)-2-methylpropyl ether, 5-phenoxybenzyl 2-(3-bromo-4-70-phenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-, (3-70-phenyl) 4-Bromophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-70rho-4-bromophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-bromo-3-chlorophenyl)- 2-Methylpropyl ether, 3-phenoxybenzyl 2-(/-bromo-3-chlorophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-fluoro-3-methylphenyl)-2-methylpropyl ether , 3-phenoxybenzyl 2-(4-fluoro-3-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-fluoro-4-methylphenyl)-2-methylpropyl ether, 6 -Phenoxybenzyl 2-(3-70rho-4-methylphenyl)-2-ethylpropyl ether, 5-phenoxybenzyl 2-(3-bromo-4-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2 -(3-bromo-4-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-diethyl-phenyl)-2-methylpropyl ether, 6-phenoxybenzyl 2-(3,4 -diethyl-phenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(
4-isopropylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-isopropylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-diinglobylphenyl)
-2-Methylpropyl ether 3-phenoxybenzyl 2-(3,4-diisopropylphenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(3,4-di-tert-butylphenyl)-2-methylpropyl Ether, 6-phenoxybenzyl 2-(5,4-di-terjariftylphenyl)-2-ethylpropyl ether, 5-phenoxybenzyl 2-(s-ethyl-4-methylphenyl)-2-methylpropyl ether , 6-phenoxybenzyl 2-(3-ethyl-4methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-ethyl-6-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2 -(4-ethyl-3-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-p-chary-phthyl-6-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2- (4-tert-phthyl-3-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(1-isopropyl-3-
) fruphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-isopropyl-3-
(methylphenyl) T2-ethylpropyl ether, etc. Next, the method for producing the compound represented by the general formula [1] of the present invention will be explained in more detail by giving synthesis examples.

Synthesis Example 1 3-(4-bromophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether Dry - Sodium hydride (6
0% in oi+ ) 0.99 was added, then 2-(
4-Chlorophenyl)-2-methylpropyl alcohol 2.8f/10rrtl acetonitrile solution at 50℃
It was dripped.

After heating under reflux for 30 minutes, 3-(4-bromophenoxy)-4-fluorobenzyl bromide 6.6f/10
rul acetonitrile solution was added dropwise over 10 minutes, and the mixture was further heated under reflux for 1 hour.

After cooling to room temperature, the mixture 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 15o7 (developing solvent: toluene/n-hexane 1:1) to obtain the desired ether 4.6S" (theoretical). Yield 65%
) was obtained.

0 nDl, 5806 i 1m νmax 1590 , 1490 , 1435 , 1
295, 1225.

1105, 1020, 830cm-'δ 1.2
9 (S, 6H), 3.32 (S, 2H),
4.32 (S, 2R).

cct.

6.7-7.5 (m, 11 H) Analysis result C2aHzxBrCtFO2 Calculated value (%) C59,56H4,56Br 17.
23C17,65F 4.10 Actual value (%) 059.85 H464Br 17
．． 01C1777F 4.00 Synthesis Example 2 3-Phenoxy-4-fluorobenzyl 2-(4-methylphenyl)-2-methylglobyl ether, heated to 2011 Ll of toluene with 0.659 sodium hydride (60% NOI+) Reflux and add 2-
(4-)f-ruphenyl)-2-methylpropyl alcohol 1.7y 725% DMF -Toluene 10m
1 solution was added dropwise over 15 minutes. After continuing stirring for 1510 minutes, 6-phenoxy-4-fluorobenzyl chloride s, af/toluene 10+1L/solution was added dropwise over 20 minutes. After further heating under reflux for 15 hours, the mixture was cooled to room temperature and drained into water.

After washing the extract with toluene and water, it was dried with Glauber's salt.

The crude ether obtained by distilling off toluene under reduced pressure was passed through a silica gel column 100. Purification was performed by column chromatography (developing solvent: toluene/n-hexane 1:1) to obtain the desired pure ether 272 (theoretical yield: 71%).

nD 15611 i1m νmax 1600, 1500, 1435, 129
0.1'225°1105, 825, 695
cm-'δ((41,30(S, (SH), 2.
27 (S, 3H) '+ 3.34 (S, 2H
), .

4.34 (S, 2H), 6.8-74 (m,
, 12H) Analysis result 024H25FO2 Calculated value (%> c 79.09 H6,91F 5
．． 21 Actual value (%) C79,23H7,01F 5
．． 42 Synthesis Example 3 3-Phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylglobyl ether 50% NaOH aqueous solution 20f, 2-(4-chlorophenyl)-2-methylpropyl alcohol6. Of.

3-phenoxy-4-fluorobenzyl bromide 86
f1 and tetrabutylammonium bromide 112
was added, and 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 over Glauber's salt, the toluene was distilled off under reduced pressure, and the resulting crude ether was subjected to column chromatography on silica gel 2502 (developing solvent: toluene/n-hexane 1:
1), the desired ether 1a, of (
A theoretical yield of 80 cm) was obtained.

0 nDl, 5710” m1585, 1490, 1425, 1280, 121
0゜ν ax 1095, 1100, 820, 685 cm-'
δ. . 4 1.26 (S, 6H), 3.30 (S
, 2H), 4.32(S, 2H).

6.8-7.4 (m, 12H) Analysis result C23H22CtF02 Calculated value □□□) C71,77H5,76C19,2
1F 4.94 Actual value (%) c 71.95 H
5,55ct 9.31 F 5.02 Synthesis Example 4 6-phenoxy-4-fluorobenzyl 2-(5-methylphenyl)-2-methylpropyl ether toluene 2 [1 mg to 2 mJ of concentrated sulfuric acid, 3-phenoxy-
4-fluorobenzyl alcohol 272.2-(3-methylphenyl)-2-methylpropyl alcohol 2.1
9 was added, and the mixture was heated under reflux for 6 hours (produced water was removed from the thread 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 purified by silica gel 1.
The resulting product was purified by column chromatography (developing solvent: toluene/n-hexane 1:1) to obtain the desired ether 1.9 F (theoretical yield: 42 H).

n2' 1.5582 i1m νmax 16oo, 1505, 1435
, 1290 , 1225 .

1130, 710 cm-' δcc4 1.30(S, 61(), 2.29(
S, 3H), 3.34 (S, 2H).

4.33 (S, 2H), 68-7.4 (m
, 12H) Analysis result 024H25FO2 Calculated value (%) C79,09H6,91F 5.2
1 actual value r%) C79,31H7,02F 5.
01 Synthesis Example 5 3-phenoxy7-4-fluorobenzyl 2-(4-1
(0)-2-methylpropyl ether 4-chloroneophyl chloride 8.53f, 5-niphenoxy-4-fluorobenzyl alcohol 8722.4
5% NaOH-3,9f and dimethyl sulfoxide 4
81 was heated and stirred at 140° C. for 3 hours. 454 NaO
H1,8S' was added, and the reaction was further continued at the same temperature for 4 hours. The reaction solution was discharged into 500 mJ of water, extracted with benzene, the benzene extract was washed with water, and then dried with Glauber's salt.

The crude ether obtained by distilling off benzene under reduced pressure was separated and purified using silica gel 250f column chromatography and tography (developing solvent: toluene/n-hexane 1:1) to obtain the desired ether 7.27f (theoretical yield). A ratio of 77% to consumed 4-chlorneophyl chloride was obtained.

n, 1,571.0 The infrared spectrum and NMR spectrum were consistent with the ether obtained in Synthesis Example 6.

Synthesis Example 6 Loophenoxy-6-chloropenzyl 2-(4-chlorophenyl)-2-methylpropyl ether 2-(4-chlorophenyl)-2-methylpropyl alcohol 2.0 fX 3-phenoxy-6-chlorobenzyl proma()" 3.5F, 50% NaOH209, toluethylbenzylammonium bromide 0.41'r
The mixture was placed in an ams sepa 2-pul flask and stirred at 50°C for 2 hours. After cooling to room temperature, the mixture was cooled with ice water, water and benzene were added, and the mixture was stirred. 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 subjected to column chromatography on silica gel 1501 (developing solvent:
The desired ether 382 (87% of theoretical yield) was obtained by purification using toluene-hexane (1:1).

n19°51.5854 i1m νmax 1500.14B0,1275,126
0,1215°1110, 1020, 830 c
m, 'δCCt, 1.29(S, (SR),
3.44 (S, 2H), 4.49 (S, 2H)
.

6.7-75 (Bow 12H) Synthesis Example 7 3-Phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2,3-dimethylbutyl. Sodium hydride (60% in o
il) 0.6Of was added and heated to reflux, and to this was added 2-(
4-10lofenyl)-2-improvyl alcohol 2
．． 0f/40ch DMF -) Toluene 10R1 solution 20
It was dripped in minutes. 7 This is true! After continued stirring for 10 minutes, 3-phenoxy-4-fluoroverdyl/romai)'
3.5 r/) Chef 10 m/solution 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 silica gel 12O2 (developing solvent: toluene-hexane 1:1) to obtain the desired ether 2,89 (theoretical yield of 72). I got it.

nDl, 5656 ”” 1610 , 1530 , 1510 , 1450
, 1300.

ν ax 1230, 1140, 1120, 1030 cm
-'δcct, 0.62 (d, 3H, J=6.
8H2), 0.85(d, 3H,J=6.8JH2
), 1.19(S,,3H), 1.9-2.3
(m, IH).

4.30 (S, 2H), 6.7~7.4 (m
, 12H) The method for producing the starting material general formula (It) will be explained in detail below using synthesis examples.

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

(1) Arylacetonitrile 10f, KOH20y.

Methyl iodide (12 molar ratio to arylacetonitrile) was added dropwise to H2O202 and triethylbenzylammonium bromide 22 over 1 to 2 hours while keeping the temperature at 80 to 90C. Next, add 2f of KOHlof, )IJ ethylbenzylammonium bromide, and at the same temperature,
The desired alkyl halide (1.2 molar ratio to arylacetonitrile) was added dropwise over 1-4 hours. After cooling to room temperature, it was extracted with toluene. The desired dialkyl form of arylacetonitrile was obtained from the toluene layer.

(2) The dialkyl form of arylacetonitrile synthesized in (1) was hydrolyzed with 50% H2SO or water bath diethylene glycol-KOH at 130 to 150'C to obtain 2-aryl-2-alkylpropionic acid.

Representative compounds are shown below.

(R)mRlmp HC! H3-75-765°C 3-CtCH3-66, 5-615°C 5.4-Cl2C! H3-93,5-945℃4-CH
2Cl2- 80~815℃4-C1C3H5-'
59-61.5℃ 4-OCR30H3-82,5-84
(3) The 2-aryl-2-alkylpropionic acid synthesized in (2) is reduced with lithium aluminum hydride in tetrahydrofuran to obtain the desired 2-alkylpropyl alcohol.

Synthesis Example 9 2-(4-chlorophenyl)-2-)thylpropyl 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,
Cushary 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-butylchlorobenzene 259 (113℃/2
8 mm Hg).

(2) After adding 25f of 4-ternary-butylchlorobenzene synthesized in (1), 20f of sulfuryl chloride, and a catalytic amount of benzoyl peroxide, the temperature was raised to 10
After keeping it at 0℃ for 1 hour, it was distilled under reduced pressure to give 2-(j4
-chlorophenyl)-2-methyl-1-chloro-propane 170 f'(121~b (3) Magnesium (turnings) 27,?, a small amount of iodine as a catalyst was added to 100 m/' of dry tetrahydrofuran, and a small amount of iodine was added under heating under reflux. 20.32 g of (4-chlorophenyl)-2-methyl-1-chloropropane was added dropwise over 30 minutes and heated under reflux for 10 hours. After cooling to room temperature, oxygen gas was blown in for 1 hour. Then, saturated ammonium chloride After adding the aqueous solution, most of the tetrahydrofuran was distilled off under reduced pressure and extracted with toluene.Toluene was distilled off under reduced pressure to obtain crude alcohol.

Next, 2-(4-chlorophenyl)-2-methylpropyl alcohol 1332, which was intended for recrystallization, was obtained from cold hexane.

mp 46-48℃ Analysis result C engineering. H13C4O Calculated value (%) C65,04H7,10C119,2
0 actual measurement value (chi) C64, 18H6, 95C119,
16 Synthesis Example 10 2-(3,4-methylenedioxyphenyl)-2-)
f-propyl alcohol was synthesized according to the following sequence.

Magnesium 7 (turnin) in 100 ml of dry ether
gs) 272, a small amount of iodine was added as a catalyst, and methyl iodide 17r was slowly added dropwise. After completion of the dropwise addition, heating and refluxing was continued for 30 minutes. Then, while increasing the temperature, benzene 10
0ml was added dropwise to replace the ether with benoze/.

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

Furthermore, after heating under reflux for 5 hours, 6N-HCl was added under cooling.
20 rul 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-methylenedioxyphenyl)-2.
-Methyl-3-butanone 1922 was obtained.

(2) Bromine 128 was added dropwise to 741 ml of sodium hydroxide, 35 ml of water, and 1 oml of dioxane at 20° C. or below.

Then, the temperature was raised to 9,000° C., and 10 g of 2-(3,4-methylenedioxy/phenyl)-2-methyl-3-furinone was slowly added dropwise thereto, followed by heating and stirring at 9° C. 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 7.5, p was obtained.

(3) 2-(3,4-methylenedioxyphenyl)-2-methylenepropionic acid synthesized in (2) above was reduced with lithium aluminum hydride in tetrahydrofuran to obtain the desired 2-(3,4- methylenedioxyphenyl)-
2-Methylpropyl alcohol was obtained.

ikn νr11aX339o, 1495.1235.1040
CI11'acc141.25 (S, 6H), 3.
59 (8, 2H), 5.87 (S, 2H), 6.6-6
．． 9 (m, 5 H) Synthesis Example 11 2-(4-difluoromethoxyphenyl)-2-methylpropyl alcohol ~ Synthesized according to the following sequence.

(1) 2.4-bis(4-hydroxyphenyl)=
After dissolving 18.0 g of 4-methy-2-pentene in 100 ml of acetonitrile, 10 g of 50% NaOH was added dropwise. Then blowing of difluorochloromethane (Freon-22) was started at a temperature of 60-70°C. When about 60 parts of the required amount for the reaction was injected (after about 20 minutes), 50
An additional 10 g of Chi-KOH was charged, and the blowing was continued.

The blowing was stopped when 1.5 times the amount of difluorochloromethane required for the reaction was blown into the reactor. After cooling to room temperature, 500 m of water
A! and extracted with toluene. After washing the toluene layer with water, it was dried with Glauber's salt, and the toluene was distilled off under reduced pressure. The crude ether obtained was purified by column chromatography using 7 Lika and Gel 200I (developing solvent: toluene) to obtain the desired product 2. 4-bis(4-difluoromethoxyphenyl)-4-methyl-2-pentene 192I was obtained.

Yield: 77 cm.

n r・' 1-5285 (2) Dissolve 2.4-bis(4-difluoromethoxyphenyl)-4-methyl-2-pente 7B,Of;l in 10011 Ll of acetone, and dissolve KMnO (
Added 30g. After stirring at 30°C for 10 hours, 20 ml of ethyl sulfol 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. Dilute Na0 in toluene layer
I [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.

Distilling off toluene under reduced pressure produces the desired 2-(4-
Difluoromethoxyphenyl)-2-methylpropionic acid 4.29.

(mp, se, s ~6.95°C). Yield 84%.

δc0'4 1.58 (S, 6H), 6.42 (t
, I H, J=75H2)1 t76(broad
s, IH) ppm (3) Tetrahydrofuran 20m
/, lithium aluminum hydride 0.5. ! 2-(4-difluoromethoxyphenyl)-2-methylpropionic acid 2. o'J/tetrahydrofuran 10m
1 solution was added dropwise at 40°0. After the dropping is completed, the temperature is raised to 6.
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-methylpropyl alcohol 1.
8g was obtained. Yield 96%.

, fllrn 536o, 1510.1680.122
0.1185, ax 115.0.1040.835Cm Synthesis Example 12 2-(4-fluorophenyl)-2-methylbutyl alcohol Synthesized according to the following sequence.

(1) 4-fluorotoluene 16.6.9. NB53
0. Og, benzoyl peroxide 0.5g 1 carbon tetrachloride 150mA! 2. Charge into a 300+al flask.
It was refluxed for 0 hours. After cooling to room temperature, the precipitate formed was removed by filtration, and the cc7!4 solution was washed with dilute alkali and water in that order, and dried with Glauber's salt. Distill the carbon chloride at the bottom under reduced pressure,
28.8 g of crude 4-fluorobenzyl bromide was obtained.

NaON 8.817, water 9. Crude bromide 2B obtained above in OllQ, 8 g/ethanol 30V! The solution was added dropwise at 70-80°C (30 minutes). Next ℃・de 8
After being kept at 0°0 for 5.0 hours, it was cooled to room temperature and drained 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 162 g of crude 4-fluorobenzyl cyanide.

f11rT''2270.1615.1520.146
0.1240, ax 21 1170.825 cm (2) Crude 4-fluorobenzyl cyanide obtained in (1) 12.81! , 50% NaOH 409, triethylbenzylammonium bromide 2.1 was placed in a flask and 14.9 methyl iodide was added dropwise with stirring (70°
C115 minutes).

After further holding at 70°0 for 50 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. Under reduced pressure, benzene was distilled off and α-methyl-
4-j fluorobenzyl cyanide 13.4.9 was obtained.

α-Methyl-4-fluorobenzyl cyanide 7.0g
, KOH159, H2O101i, triethyl 2.0g of rubenzylammonium bromide was charged into a flask, and 10ml of ethyl bromide was added dropwise at 80°C for 11 hours while stirring.Next, the temperature was kept at the same temperature for 2 hours.Following operations is as described above. Crude α-ethyl α-
7.9 g of methyl-4-fluorobenzyl cyanide was obtained.

Crude α-ethyl-α-methyl-4-fluorobenzyl cyanide 7,69, 20 ml of H2O, and concentrated sulfuric acid 20 resistant were charged into a flask and heated at 134 to 137°C for 5.5 hours and 9 hours! It flowed. 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 7.5 with concentrated hydrochloric acid, and extracted with benzene to remove impurities. Then, the aqueous layer was adjusted to pH 4.6 with concentrated hydrochloric acid 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 38 Il of 2-(4-fluorophenyl)-2-methylbutyric acid.

20 times 30.85 (t, 3H, J = 7 horses), t55 (8
, 3H), 1.8-2.3 (m, 2l-1), 7.0
~7.6 (m, 4H), 11.3 (broal 8.
IH) (5) Tetrahydroflough 20ml 1. A 3.09/f VOml solution of 2-(4-fluorophenyl)-2-methylbutyric acid in trahydrofuran was added dropwise to a mixture of 0.59% lithium aluminum hydride at 40°C. After the dropwise addition was completed, the temperature was raised and refluxed for 30 minutes. After cooling to room temperature,
Excess lithium aluminum hydride was separated by dropwise addition of ethanol, and water was further added to completely decompose it. The formed precipitate was removed by filtration, and tetrahydrofuran was distilled off under reduced pressure. After extracting with pen and zene and washing the benzene layer with water,
Dried with Glauber's salt. Benzene was distilled off under reduced pressure to obtain the desired 2-
2.69 g of (,4-fluorophenyl)-2-methylbutyl alcohol was obtained.

3 nDl, 5055 i1m νmax 3360.1610.1520.1240
．． 1175.1040.840 cm Synthesis Example 13 2-(a-Methylthiophenyl)-2-methylpropyl-alcohol Synthesized according to the following sequence.

(1) Synthesis of 4-methylthiobenzyl chloride Methyral 18.2g 1.2-') Chlorethane 20011
/! Anhydrous aluminum chloride 61.411 was added while cooling with water. Add 24% of thioanisole to this.
8.9 was added dropwise at room temperature, and the mixture was stirred for 3 hours to react. After the reaction was completed, the mixture was poured into water and concentrated hydrochloric acid was added to dissolve the solids, followed by extraction with benzene, and the extract was washed with water, cooled sodium hydrogen oxide solution, and water. After drying with Glauber's salt, the solvent was removed to obtain 607 g of an oily residue.

(2) Synthesis of (4-methylthiophenyl)-acetonitrile 10.5 g of soda cyanide is dissolved in 12 g of water and heated to 600C. To this was added dropwise 30.79 g of the oil obtained in (1) above dissolved in 35 +++ l of ethanol, and the mixture was refluxed for 4 hours to react. The product was treated in a conventional manner and separated by column chromatography using benzene as a developing agent to obtain 14.7 g of (4-methylthiophenyl)-acetonitrile (oil).

δCCl4 2.67 (S, 3H), 3.56 (
S, 211), 7. L6(S,4H) (3) Synthesis of 1-(4-methylthiophenyl)-1,1-dimethylacetonitrile In the same manner as in (1) of Synthesis Example 10, 139 g of (4-methylthiophenyl)-acetonitrile was prepared from 131 g. Obtained the object.

δccm 1.66 (S, 6H), 2.45 (S, 3
H), Z2~Zs(m, 4H) (4) Synthesis of t-(4-methylthiophenyl)-1-methylpropionic acid Caustic potash 5.09. 5g water, 2g diethylene glycol
Add 68g of 1-(4-methylthiophenyl)-1,1-dimethylacetonitrile to 0ml, and add 130~1. A-
/6°0 for 7 hours. After the reaction was completed, it was cooled, drained into water, and extracted with benzene. When the aqueous layer was acidified with concentrated hydrochloric acid, a precipitate was deposited. This was extracted with ether, washed with saturated saline, dried with Glauber's salt and deoxidized, and the solid 1-(
4-Methylthiophenyl)-1-methylpropionic acid in 1. 'I got 9g.

δ Acetone d6 1.54 (S, (SH), 2.
43(S, 3H), 70-7.5(m, 4H) (5)'Synthesis of 2-(4-methylthiophenyl)-1-methylpropyl alcohol Reduction with lithium aluminum hydride in the usual manner yields 1-( 4
-methylthiophenyl)-1-methylpropionic acid 1.
1.5 g of the target alcohol was obtained from 9 g.

δcc14t26(s, 6H), 2.39(8,3H
), 338(8,2H), 70-Z4(m, 4H) Synthesis Example 14 Synthesis of 2-(4-chlorophenyl)-2-methylpropylthiol Synthesis was performed according to the following sequence.

(1) Synthesis of 2-(4-chlorophenyl)-2-methylpropyl tosylate Add 20 ml of pyridine to 10.0,9 2-('4-chlorophenyl)-2-methylpropyl alcohol and 108 g of p-toluenesulfonyl chloride. , 50~55°
The reaction was carried out at 111r at C. The reaction product was poured into 100 g of ice water, and acidified with dilute hydrochloric acid (11° benzene extraction). 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 white solid residue of 193I. Melting point 69-71.5°C δCCl4 1.31 (S, 6) (), 2.44 (
s, 3H), Ro89 (S, 2H), 7.13 (S, 4
1■), 718~76゜(m, 4H(AB Type
)]va1595.1480.1355.1175
．． 97o1825Cm'' (2) 13.0g of tosylate obtained in synthesis (1) of bis-(2-(a-chlorophenyl)-2methylpropyl)disulfide and 20.0.9g of sodium hydrogen sulfide (70.0g)
The reaction mixture was stirred with 1001 nl of 90% ethanol and reacted for 3 hours under reflux. The reaction product was poured into water, extracted with benzene for 5 hours, and the benzene layer was washed with water and dried with Glauber's salt. Benzene was distilled off under reduced pressure to obtain a liquid residue 79y. This was separated by silica gel column chromatography using a mixed solvent of benzene-hexane (1:5) to obtain the desired product 5.3, p (oil).

112'0.1105.1020.860.755cm
-δ"'4111 (S, 6H), 2.81 (8, 2
H), 118 (d, 4H) Elemental analysis OHS O1 Calculated value 60.17 6.01 16.06
17.76 Measured Value 59. '06 6.07 1
6.55 17.56 (3) Synthesis of 2-(4-chloro6phenyl)-2-methylpropylthiol 0.095 g of lithium aluminum hydride is suspended in 25 mA' of dry ether, and 10i+A! Bis-(2-(4-chloro7enyl)-2- dissolved in ether of
Methylpropyl]cisulfide toy was added dropwise, and the mixture was allowed to react under reflux for 2 hours. After the reaction was completed, the reaction product was poured into water, 15% diluted sulfuric acid was added, and the mixture was extracted with benzene. The benzene layer was washed with saturated brine, dried over sodium sulfate, and the solubilizer was distilled off under reduced pressure to obtain liquid residues I, Og.

νf+lrn 2965.2570.1495.140
5.1390, Dragon X 1370.1105.1020.830cm-'acc
140.80 (t, IH), 135 (S, 6H)
, 268 (d, 2H), 7.23 (S, 4H) Compounds 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 and acaricidal composition of the present invention is that
It has a broader insecticidal spectrum and synergistically enhanced insecticidal efficacy compared to when the compounds shown in the table are applied alone. That is, the composition of the present invention is effective against agricultural, horticultural and forest pests that cause damage to paddy rice, field crops, cotton, fruit trees, forests, etc. (e.g., leafhoppers, grasshoppers, grass weevils, rice weevils, rice weevils, stink bugs, aphids). , green caterpillars, armyworms, mealybugs, cutworms, grain flies, sink beetles, scale insects, leaf moths, spider mites, American white-winged wigeons, Japanese snail moths, bark beetles, nematodes, thurilapsae, etc.) as well as brown weevils, snail beetles, etc. Storage pests, flies,
It has a control effect at low concentrations against a wide range of pests, including sanitary pests such as cockroaches and cockroaches.

2nd!17) Features of the composition of the present invention are organophosphorus insecticide,
It has remarkable insecticidal and acaricidal effects even against pests that have already developed resistance to acaricides and/or carbamate-based insecticides and acaricides, and has drug-resistant properties against various pests. It means having a certain characteristic.

The sixth feature is that the composition of the present invention has fast-acting properties not found in general organophosphorus insecticides, acaricides, and carbamate insecticides and acaricides, and can be used within a short period of time after spraying. In addition to being able to make the pests fall and turn upside down, they also cause the surviving larvae to undergo metamorphosis and die, which is an action that conventional drugs do not have.

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's true.

When actually applying the composition of the present invention, it is sufficiently effective even if the composition itself is diluted, but it is generally applied after dilution.

The formulation of the composition of the present invention does not require any special conditions and can be prepared using methods well known to those skilled in the art, such as general agricultural chemicals and epidemic prevention drugs, such as milklosol, thermal fumigants (mosquito coils, electric It can be adjusted to any dosage form, such as a fog agent for mosquito repellent, etc.), a fog agent for fogging, a non-heating fumigant, a poisonous bait, etc., 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, old [A, etc.],
Bisphenol derivatives, phenyl α-naphthylamine,
By adding an appropriate amount of amyl aminos or benzophenone compounds such as phenyl β-naphthylamine or a condensate of phenetidine and acetone as a stabilizer, a composition with improved effectiveness can be obtained.

Further, for the purpose of obtaining a multi-purpose/II drug, the composition of the present invention may be used by adding an attractant, a repellent, a fungicide, a herbicide, a plant growth regulator, a fertilizer, etc.

In the composition of the present invention, the composition ratio of the compound of general formula [I] and the drug that causes abnormal metamorphosis in arthropods 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 s = 's O% for emulsions, 03 to 3% for powders, 5 to 50% for irrigation agents, and 05 to 5% for granules (all 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."

In the formulation examples, "compounds in Table 1" refer to any one of the compounds in Table 1, and chitin synthesis inhibitors refer to any one of the compounds in Table 1 at pH 604.
0,0GA-19255, juvenile 1 anti-juvenile hormone active substance, R-20458, aldocyto, prefusen■
to show offense. In addition, the kitin synthesis inhibitor and the juvenile 0 anti-juvenile hormone active substance are collectively referred to as insect growth inhibitory substances.

Formulation Example 1 5 parts of the compound shown in Table 1, 10 parts of a chitin synthesis inhibitor, 5 parts of the emulsifier Tsurupol 8M-20a (trade name of Toho Chemical), and 80 parts of xylene are stirred and mixed to prepare an emulsion.

Formulation Example 2 5 parts of the compound of Table 1, 1 part of juvenile and anti-juvenile hormone active substance
1 part, Sorbo, 5M-2005 parts, and 89 parts of xylene were mixed to prepare an emulsion.

Formulation Example 3 05 parts of the compound shown in Table 1 and 15 parts of a chitin synthesis inhibitor are dissolved in acetone, 98 parts of clay for powders are added, and the mixture is stirred to evaporate the acetone to obtain a powder.

Formulation Example 4: 0.5 part of the compound shown in Table 1 and 0.3 part of the juvenile 0 anti-juvenile hormone active substance were dissolved in acetone, and 0.5 part of the compound shown in Table 1 was dissolved in acetone.
After stirring, the acetone is evaporated to form a powder.

Formulation Example 5 Add 7 parts of a chitin synthesis inhibitor to 3 parts of the compound in Table 1 and prepare 1.
5 parts of emulsifier Tsurupol 355TLL (trade name of Toho Kagaku) are added, and after stirring, 85 parts of 00 mesh diatomaceous earth are added, and the mixture is thoroughly stirred and mixed in a Raikai machine to obtain a wettable powder.

Formulation Example 6 6 parts of the compounds in Table 1 plus 0 anti-juvenile hormone active substance and 1 part anti-juvenile hormone active substance.
After adding 5 parts of Tsurupol 355TLL and stirring, 91 parts of diatomaceous earth of 300 mesh was added and thoroughly stirred and mixed in a Raikai machine to prepare an irrigation agent.

Formulation Example 7 6 parts of the compound in Table 1, 8 parts of chitin synthesis inhibitor, and 8 parts of clay
5 parts of Toyolignin OT (trade name of Toho Chemical Co., Ltd.) and 4 parts of the mixture were added and mixed, water was further added, and after stirring and mixing, the mixture was granulated using a granulator and dried to form a powder.

Formulation Example 8 3 parts of the compound in Table 1 plus 0 anti-juvenile hormone active substance and 1 part anti-juvenile hormone active substance.
1 part, 92 parts of clay, and 4 parts of Toyolignin CT are added and mixed, water is further added, and after stirring and mixing, the mixture is granulated using a granulator and dried to form granules.

Formulation Example 9 To 1 part of the compound in Table 1, add either 3 parts of a chitin synthesis inhibitor or 0.2 parts of a juvenile anti-juvenile hormone active substance, dissolve in white kerosene to make a total of 100 parts, and mix with an oil solution. do.

Formulation Example 10 Insect growth inhibitory substance 0, 29 in compound 0.217 of Table 1
0.9 p of synergist and BHT O, 5,9 were added and dissolved in 20 ml of methanol, each carrier for mosquito coil (a mixture of tab powder, lees powder, and wood flour in the ratio of 3:5:1) 99 .4
After evaporating the methanol, add 150 d of water, mix thoroughly, and mold and dry to obtain a mosquito coil.

Formulation Example 11 Compound 0.1,9 in Table 1, insect growth inhibitory substance 0.1g
, synergist t 09KBHT O,2I! was added, dissolved in chloroform, and adsorbed onto f paper with a thickness of Q, 3 cm.
The fiber fumigation composition is heated on an electric heating plate.

Formulation Example 12 0.1 part of the compound shown in Table 1, 0.1 part of insect growth inhibitory substance,
Mix and dissolve 0.3 parts of synergist, 7 parts of Kijirole, and 7.5 parts of deodorized kerosene. Fill this into an aerosol container and attach the pulp. 80 parts of a propellant (liquefied petroleum gas) is injected under pressure through the lubricant to form an aerosol.

Formulation Example 15 0.1 part of the compound shown in Table 1, 01 part of insect growth inhibitor, 0.3 part of synergist, 11.5 parts of deodorized kerosene, 6 parts of emulsifier Atmos
00 (trade name registered by Atlas Chemical Co.) and 50 parts of pure water were added to emulsify the mixture. This is filled into an aerosol container with 37 parts of a 3:1 mixture of butane bromide and deodorized propane to form a water-based aerosol.

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

1. Hffrliptera (Hemiptera) Neph
otettix cincticeps Uhler
(Sogatella furcifera) j) rv
ath (white-tailed planthopper) Nilaparvata l
ugens 8tal () Biiro/Power) Laod
elphax 5triatellus Fal14
(Eurydcma rugosa)
Motschulsky (nagame) Eysarcor
ia parvus Uhler
(Lagynotmus elon)
gatus Dallas (rice stink bug) Noza
ra viridula Llnnc (Southern green stink bug) 01etus trigonus Thut+
erg stephanitis
nashi Esaki et Takeya Stephanitis pyrioides 5co
tt (Tsutsuji Gunbai) P syl Ia pyri
suga Fi5rster - (pear pear) P
ayllamali Schnidberger (apple psyllium) Aleurolobus taonab
ae kuwana, (grape whitefly) D+a1
curodes cstrI Ashread Trialeurodes vaporraiorum
westxvood Aphis gossypt+ alover Brevicoryne brassic
ae Linn& (radish aphid) Myzus persicae 8ulzer (peach aphid) TLlnpalosiphum m
aidis pitch, (millet aphid) xcerya purchasi Maskell (
1'1anococcujl citri R15so
(citrus mealybug) Unaspis yanonensis Kuwana
(Lepidoptera) 2, Lepidoptera (Lepidoptera) aane
phora asiatica staudinger
(Minoga) Spulerina astaurcta
Meyrick (Nashihosoga) Litbocoll
etis ringoniella Matsumur
a (ki/monhosoga) Plutella xylostella Llnn
e (diamond moth) promalactis inopis
ema Butler (ry Tamiga)Adoxoph
yes orana F 1scher von Bo
slerstanm (':l Hakumon Hamaki) Bactra furfurana Havio 100h (
Leguminivora gly
ciniborella Matsumura (?Meshinkuiga) Onaphalocrocismedinalis o
uen6e (:lbu/Me・(ga) Etiella zinckenella Treat
schke (Ogtrinia furnacalis Guene)
e (7'7 Nomeiga) Pleuroptya der
ogata' Fabricius H
yphantria cunea Drury Atraxas m1randa B
utler Lymantr
ia dispar japonica Motsch
ulsky (-qimaiga) Yachihoko) Agrotis segetum Denis et
5chiffer rrt+l Ier (Kaburayaga) uelicoverpa armigera HThb
ner (Pseudaletia) 5
eparataWalker Mame
Stra brassicae Linne (Y) Uga)P 1usia nigrisigna Walk
er (Kumanaginuwaba) 8podoptera l
1tura Fabl 1cius, Parnara guttata Bremer
et Gray (rice stink bug) p 1eris rapae cruciAra no
i 5duval (Mo:y shochiyo) Ohilo 5uppressalis, Walker
(= Cameiga) ro, □o1eopter, + (Coleoptera) Melanotus fortnumi aan
deze (? Rukubikushiko plating) Anthrenus verbasci Llnnc
(Tenebroides mauritanicus)
Linn6 (Kokunust) Lyctus brunn
eus S tephens (H)H
enosepi Iachna vigintioct
opunctata Fabl 1cius) h[onochamus alternatus Ho
pe (-r) Xylotrechus pyrrhoderus B
ates (grape beetle) Aulacophora femoralis Mot
schulsky Oulerna or, yzae Kuwayama
(Rice beetle) Phyllotreta 5tr
iolata Fabliciu5 (Il-striped flea beetle) aallosobruchus chinensis
Llnnc (Azuki weevil) Bchinocnerr+ls squareeus B
Bllber (rice weevil) 8itophilus oryzae Linne (
:I:I whale) Apoderus erythrog
aster yollenhoven Rhynchites he, ros Roelofs
(Momochokkiri weevil) Anomala cuprea Hope (Douganepuipui) 'popi IN' japonica N
ewrr+j! n (mamekogane) 4, nymen
optera (Hymenoptera) Athalia rosa
e japonensis Rokrwer Arge 51mlis Vollenhoven
(Rurichu range) 5, n 1ptera (
Diptera) Tipula aino Alexander
(Kiryujigagampo) Oulex pipiens
Aedes adlypti LinrnG Asphondylia sp, (Ylemya antiqua M)
eigen (onion fly) Hylemya pla
tura Meigen Musca d
orrlstica vicina Macquart
(housefly) nacus cucurbitae c
ahlorops o
ryzad Matsumura A
gromyza oryzae Mur+akata
(Rice leafminer) 6, S 1phonapte
ra (Hymenoptera) Pulex 1rritans L
inne (human flea)Xenopsylla che
opis Bothschild Otenocephalides canis Cur
tis (dog flea) 7, T hysanopte
ra (Hymenoptera)8circothripSdors
alisHood Tbrips tabaci Lirxleman (
8, Anoplur, a (Pediculus humanus cor)
poris De oeer (Pet louse) phthi'rus pubis Linne (Popular louse) Haematopinus eurystcrn
us N1tzsh (maggot lice) 9, P 5o
coptera Trogjum
pulsat6riun Linn6 (:7nachatatem I-Meji) Liposcelis bostrychophilu
s nadonnel (Hiratachatate) 10, 0rthhoptera (Orthoptera) Gryl
lotalpa africana palisot
de Beafvois (kera) Locusta migratoria danica
Linn6 () Oxyayezoensis 5hiraki (Kobaneigo) 11, Dictyoptera (Dictyoptera) Blattella germanica 'i
, inn/e (German cockroach).

Periplaneta fuliginosa 5e
rville (black cockroach) 12, Acarina (acariformes) noophi
Ius m1croplus c3anestrini
(Owshi r mite polyphagotarsone
Mus Iatus Banks Panonychus cit'ri
r (citrus spider mite) Tetranychus ci
nnabarium Boisduval (= Senamino 1 mite) Tetranychus urticae xoch,
(Two-spotted spider mite) 2) Next, the effects of the composition of the present invention as an insecticide and acaricide will be explained in more detail by giving test examples.

Test Example 1 Effect on Spodoptera spp. In a polyethylene cup with a diameter of ID cm, put the upper leaves of P. elegans and 10 3rd instar larvae of Spodoptera spp., and mix the compound shown in Table 1 alone or the compound and an insect growth inhibitor at a ratio of 1:2. The resulting emulsion was prepared according to Formulation Example 1. Lech was diluted with Houzhang water to give a concentration of 20 ppm, and 5 ml of the emulsion was sprayed into each cup using a scattering tower.

After the treatment, the cups were left in a constant temperature room at 25°C, and the mortality rate was determined over time. The results are shown in Table 2. In either case, there was no difference between the 1st and 7th days after the single treatment, but the mortality rate gradually increased in the mixed treatment, reaching almost complete death on the 5th day.

Table 2 1 606060 '151) 50 70 9
01004 40404040 40 '7010
01+J+]10 50505060 5050
701001670808080 80100100
10021 80909090 90100100
10029 80100100100 10010
0100 10030 70 808ff 80
6090100 10053 50 60
60 60 50 70 80 1[Jt
J59 40404050 404050 100
41 20 20 30 50
20 30 30 10042 808090
90 808090 10044 1010
1010 010 10 10048
30503030 3040100 10051
70808080 80100100 10+]5
4 0000 00307058 4040
5050' 5050 90 906D
D lj 0 0 0 10
10 7072 20 30 30 30
30 30 60 10078 80 8
0 80 80 80 100 100 100
79 90 100100100 100 10
0 100 401181 5+1 50 505
0 50 60 90-10084 20
50 30 30 20 40 60 1
0087 30 30 5[] 30 30
30 70 10091 50 60 60
60 (So 711 9 (1,10G control Laiqi) pH 6040 10102040 Test Example 2 Two-spotted spider mite larvae were released onto a bean leaf disk with a diameter of 15 fins, and emulsion 5me similar to Test Example 1 was sprayed, and the mortality rate was measured over time. Calculations showed that in the case of the compound shown in Table 1 alone, the mites survived and 10 to 30% became adults, whereas in the case of the mixed treatment, the mites were completely killed on the 6th day.

Test Example 5 Effect on resistant leafhoppers Rice seedlings (2 to 6 leaves) were hydroponically cultivated in pots with a diameter of 5 c+n, and each test compound and drug monomer were grown using the method shown in Formulation Example 1. A 10 ppma chemical solution of the agent and the mixture was treated using a sprayer at a rate of 5 ml/bot.

After air-drying, the seedlings were covered with a wire mesh cylinder, and 10 larvae of the resistant leafhopper (native to intercultivation) were released per pot.
It was left standing in a room at °C. After 24 hours of treatment, the number of live and dead vehicles was investigated, and the mortality rate was calculated. The results are shown in Table 3 as three consecutive average values.

Table 3 No. 1st day 3rd day 7th day 1st day 3rd day 7th day 1 70 80
80 70 90 1004
30 50 40 30 80
1001'0 50 50 50
40 70 10016 50
50 50 50 60 1
0021 70 70 80 80
100 1o029 100 100
1 勺ioio 1oo'io.

30 30 40 40 2
0 40 9033 20 40
40 20 50 10059
40 40 50 50
70 10041 10 20
20 10 50 8042, 7
0 80 80 80 1oo 10044
20 20 20 20 4
0 10048 40 40 40
50 70 10051 80
80 80 90 100;
L) 954 90 100 100
100 100 1005B 20
20 20 20 60 8065
B[) B[l 80
80 10[11[][]72 30 4
0 40 20 60 9078
100 100 10L] 100
100 10079 100 100
100 100 100 10081
10 80 80 90 100 10
084 50 50 60 4
0 714 10087 60 60
60 70 100 1[]091
9Cj 1 10 100
1L] 0 100 10+1 Control drug pH6o4o 0 5 5 Test example 12.3
As a result of testing chitin synthesis inhibitors other than pH 6040 listed in Kikiri A1, juvenile hormone active substances, or mixtures of anti-juvenile hormone active substances and compounds listed in Table 1 in the same manner as above, In Test Example 12.3, the same insecticidal and acaricidal effects as y were obtained.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] General formula [In the formula, Ar is a IJ -/Shi group, R is a hydrogen atom,
methyl group or ethyl group, R2 is a straight chain or branched alkyl group having 1 or more carbon atoms, R3 is a hydrogen atom, halogen atom, lower alkyl group or lower alkoxy group, R
4 represents a hydrogen atom, ), a rogen atom, a lower alkyl group or a lower alkoxy group, respectively. X represents an oxygen atom or a sulfur atom. ] One type of 2-arylethyl ether or thioether derivative represented by 2
1 of the drugs that cause abnormal metamorphosis in species and arthropods
An insecticidal and acaricidal composition comprising one species or two or more species.