JPH0231684B2 - SATSUCHUSATSUDANISOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

The present invention is a novel compound having the following general formula: [Wherein, Ar is a lower alkyl-substituted naphthyl group, an unsubstituted phenyl group, a halogen atom at the 4-position, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group,
a phenyl group substituted with a cyano group or a nitro group,
In addition to the 4-position, the 3-position is a phenyl group substituted with a halogen atom, a lower alkyl group, or a lower alkoxy group, or a phenyl group substituted with a methylenedioxy group, R ₁ is a methyl group or an ethyl group,
R ₂ is a methyl group, ethyl group or isopropyl group, R ₃ is a hydrogen atom or a halogen atom, R ₄ is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 2 carbon atoms, or a lower alkoxy group having 1 to 2 carbon atoms. Each represents a group. X represents an oxygen atom or a sulfur atom. ], and one or more 2-arylethyl ether derivatives or thioether derivatives, 1-naphthyl methyl carbamate (NAC), m-tolyl methyl carbamate (MTMC), O-cumenyl methyl carbamate (MIPC), O- sec-Butylphenylmethylcarbamate (BPMC) O-isopropoxyphenylmethylcarbamate (PHC) 3,4-xylylmethylcarbamate (MPMC) 3,5-xylylmethylcarbamate (XMC) Common names are in parentheses. show. The present invention relates to an insecticidal and acaricidal composition containing one or more carbamate-based insecticides and acaricides. Conventionally, as agricultural and horticultural insecticides and epidemic prevention insecticides, for example, S-[1,2-bis(ethoxycarbonyl)ethyl]dimethylphosphorothioate (Marathon)
Dimethyl-4-nitro-m-tolyl-phosphorothioate (MEP) Diethyl-2,3-dihydro-3-oxo-2
-Phenyl-6-pyridazinyl phosphorothioate (pyridafenethione) Diethyl-2-isopropyl-6-methyl-4
-Pyrimidyl-phosphorothioate (Diazinon) O,S-dimethyl-N-acetylphosphoroamidothioate (acephenate) Dimethyl-S-(N-methylcarbamoylmethyl)phosphorothiolthioate (dimethoate) 1-Naphthylmethylcarbamate (NAC) ) m-Tolylmethylcarbamate (MTMC) 2-dimethylamino-5,6-dimethylpyridin-4-yl-dimethylcarbamate (pyrimer) 3-Methyl-N-(methylcarbamoyloxy)
Insecticides such as thioacetimidate (lannate) have been used. These insecticides and acaricides have properties such as fast-acting, systemic transferability, and gas effect.
Although some have excellent properties, they are not all satisfactory in terms of insecticidal spectrum, residual efficacy, fish toxicity, human toxicity, etc. 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 diamondback moths, sanitary pests such as house flies, and spider mites that damage various crops have developed remarkable drug resistance. Carbamate-based insecticides and carbamate-based insecticides are losing their practicality. Furthermore, introducing large amounts of these chemicals into fields causes environmental pollution of soil, rivers, etc., which is a problem, and there is a strong desire for control using low dosages. The novel compounds of the present invention represented by the above general formula [] satisfy these requirements and have insecticidal and acaricidal activity even on their own, but the present inventors have further investigated the actual use of these compounds. As a result of various studies to improve the control effect and reduce the amount used, we found that by applying a mixture of the compound represented by the general formula [] and one or more carbamate insecticides and acaricides. The present invention was completed based on the discovery that the insecticidal spectrum is broadened and the insecticidal activity is synergistically enhanced compared to when applied alone. Next, representative examples of the compounds represented by the general formula [] of the present invention and their physical properties are shown in Table 1 below.

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[Table] The compound represented by the above general formula () is a new compound, and examples of its synthesis are shown below. The compound represented by the general formula [] is the compound represented by the general formula [] The compound represented by the general formula [] [In these formulas, Ar, R ₁ , R ₂ , R ₃ , and R ₄ each represent the above-mentioned meanings, and one of the groups A and B represents a halogen atom, and the other group represents an X-
Reacting with a compound represented by the group M (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] obtained by. 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, the compound of the present invention has an asymmetric carbon when R ₁ and R ₂ are different groups in the general formula [], and optical isomers exist, but mixtures of these optical isomers and these components It includes. 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-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-methoxyphenyl)-2-methylpropyl ether and thioether , 3-phenoxy-4-fluorobenzyl 2-(3,4-dimethylphenyl)
-2-Methylpropyl ether and thioether, 3-(4-fluorophenoxy)-4-fluorobenzyl 2-(4-methoxyphenyl)-2-
Methyl propyl ether and thioether, 3
-Phenoxy-4-fluorobenzyl 2-(4
-chlorophenyl)-2-ethylbutyl ether and thioether, 3-phenoxy-6-chlorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-
(4-fluorophenoxy)-4-fluorobenzyl 2-(3,4-dichlorophenyl)-2-methylbutyl ether and thioether, 3-(3-
chlorophenyl)-4-fluorobenzyl 2-
(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-(3-chlorophenoxy)-4-fluorobenzyl 2-(3,4-
dimethylphenyl)-2,3-dimethylbutyl ether and thioether, 3-phenoxy-4
-fluorobenzyl 2-(4-chlorophenyl)
-2-Methylpropyl ether and thioether, 3-(2-fluorophenoxy)-4-fluorobenzyl 2-(3,4-dichlorophenyl)-
2-Methylpropyl ether and thioether, 3-(2-fluorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-
Phenoxy-4-fluorobenzyl 2-(4-
tert-butylphenyl)-2-methylpropyl 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- Bromophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-5-fluorobenzyl 2-(3,4-diethylphenyl)-
2-Methylpropyl ether and thioether, 3-(3-fluorophenoxy)-4-fluorobenzyl 2-(3-methoxy-4-methylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluoro Benzyl 2-(3-ethoxy-4-bromophenyl)
-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2
-(4-chlorophenyl)-2-methylbutyl ether and thioether, 3-phenoxy-4-
Fluorobenzyl 2-(4-difluoromethoxyphenyl)-2-methylpropyl ether and thioether, 3-(3-methylphenoxy)-
4-fluorobenzyl 2-(4-chlorophenyl)-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-methoxyphenyl)-2-methylpropyl ether and thioether, 3-phenoxy- 6-bromobenzyl 2-(4-methylphenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoxy)-4-fluorobenzyl 2
-(3,4-dichlorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-2-fluorobenzyl 2-phenyl-2-methylpropyl ether and thioether, 3-
Phenoxy-4-fluorobenzyl 2-(4-
chlorophenyl)-2,3-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-fluoro phenoxy)-5-fluorobenzyl 2-
(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-
Fluorobenzyl 2-(4-fluorobenzyl)
-2-methylpropyl ether and thioether, 3-phenoxy-5-fluorobenzyl 2-
(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-2-
Fluorobenzyl 2-(4-trifluoromethylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-nitrophenyl)-2-methylpropyl ether and thioether, 3-phenoxy- 5-chlorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-6-chlorobenzyl
2-(4-methylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-
6-fluorobenzyl 2-(4-methoxyphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(3,4-methylenedioxyphenyl)-
2-Methylpropyl ether and thioether, 3-phenoxybenzyl 2-(4-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(bromophenyl)
-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-chloro-4
-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,4-dibromophenyl)-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-(4-fluorophenyl)-2-methylpropyl ether Sibenzyl 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-ethylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-dichlorophenyl)-2- Ethylpropyl ether, 3-phenoxybenzyl 2-(4-chloro-3
-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-tert-butylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-dimethylphenyl)- 2-methylpropyl ether, 3-phenoxybenzyl 2-(3-chloro-4
-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 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-chlorophenyl)-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
-fluorophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,4-difluorophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,4-difluorophenyl)-2- Ethylpropyl ether, 3-phenoxybenzyl 2-(3-bromo-4
-fluorophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3-bromo-4
-fluorophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-fluoro-4
-bromophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3-fluoro-4
-bromophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-bromo-3
-chlorophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-bromo-3
-chloro-phenyl)-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, 3-phenoxybenzyl 2-(3-fluoro-4
-methylphenyl)-2-ethylpropyl ether, 3-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, 3-phenoxybenzyl 2-(3,4-diethyl-phenyl) )-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-isopropylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-isopropylphenyl)-2-ethylpropyl Ether, 3-phenoxybenzyl 2-(3,4-diisopropylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,4-diisopropylphenyl)-2-ethylpropyl ether, 3-Phenoxybenzyl 2-(3,4-di-tert-butylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,4-di-tert-butylphenyl)- 2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-ethyl-4
-methylphenyl)-2-methylpropyl 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-tert-butyl) -3-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-isopropyl-3-methyl-phenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-isopropyl -3-methylphenyl)-2-ethylpropyl ether, etc. Next, the above general formula of the present invention []
The method for producing the compound represented by will be explained in more detail by giving synthesis examples. Synthesis Example 1 3-(4-bromophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether 0.9 g of sodium hydride (60% in oil) was added to 20 ml of dry acetonitrile, and then 2- (4-chlorophenyl)-2-methylpropyl alcohol 2.8
g/10ml acetonitrile solution was added dropwise at 50°C. After heating under reflux for 30 minutes, 3-(4-bromophenoxy)-4-fluorobenzylbromide 6.6
g/10ml acetonitrile solution was added dropwise over 10 minutes,
Further, the mixture was heated under reflux for 1 hour. After cooling to room temperature,
It was drained 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 subjected to column chromatography on 150 g of silica gel (developing solvent: toluene/n-hexane 1:
1) to obtain 4.6 g (theoretical yield: 65%) of the desired ether. n ²⁰ _D 1.5806 ν ^film _nax 1590, 1490, 1435, 1295, 1225, 1105,
1020, 830cm ^-1 δ _ccl4 1.29 (S, 6H), 3.32 (S, 2H), 4.32 (S,
2H), 6.7-7.5 (m, 11H) Analysis result C ₂₃ H ₂₁ BrClFO ₂ Calculated value (%) C 59.56 H 4.56
Br 17.23 Cl 7.65 F 4.10 Actual value (%) C 59.85 H 4.64
Br 17.01 Cl 7.77 F 4.00 Synthesis Example 2 3-Phenoxy-4-fluorobenzyl 2-
(4-Methylphenyl)-methylpropyl ether Sodium hydride (60% in
0.63 g of oil) was heated to reflux, and 1.7 g of 2-(4-methylphenyl)-2-methylpropyl alcohol was added to this.
g/25% DMF-toluene solution (10 ml) was added dropwise over 15 minutes. After continuing stirring for 10 minutes, 3-
Phenoxy-4-fluorobenzyl chloride
A solution of 3.0 g/10 ml of toluene was added dropwise over 20 minutes.
After further heating under reflux for 1.5 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 toluene off under reduced pressure was purified by column chromatography on a 100 g silica gel column (developing solvent: toluene/n-hexane 1:1) to obtain the desired purified ether.
2.7 g (71% theoretical yield) was obtained. n ²⁰ _D 1.5611 ν ^film _nax 1600, 1500, 1435, 1290, 1225, 1105,
825, 695cm ^-1 δ _ccl4 1.30 (S, 6H), 2.27 (S, 3H), 3.34 (S,
2H), 4.34 (S, 2H), 6.8-7.4 (m, 12H) Analysis result C ₂₄ H ₂₅ FO ₂ Calculated value (%) C 79.09 H 6.91 F 5.21 Actual value (%) C 79.23 H 7.01 F 5.42 Synthesis implementation Example 3 3-phenoxy-4-fluorobenzyl 2-
(4-chlorophenyl)-2-methylpropyl ether 50% NaOH aqueous solution 20g, 2-(4-chlorophenyl)-2-methylpropyl alcohol 6.0g, 3
-Phenoxy-4-fluorobenzyl bromide
8.6 g and 1.1 g of tetrabutylammonium bromide were 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 purified by column chromatography using 250 g of silica gel (developing solvent: toluene/n-hexane 1:1) to obtain the desired product. Ether 10.0g (theoretical yield
80%). n ²⁰ _D 1.5710 ν ^film _nax 1585, 1490, 1425, 1280, 1210, 1095,
1100, 820, 685cm ^-1 δ _ccl4 1.26 (S, 6H), 3.30 (S, 2H), 4.32 (S,
2H), 6.8-7.4 (m, 12H) Analysis result C ₂₃ H ₂₂ ClFO ₂ Calculated value (%)
C 71.77 H 5.76 Cl 9.21 F 4.94 Actual value (%)
C 71.95 H 5.55 Cl 9.31 F 5.02 Synthesis Example 5 3-Phenoxy-4-fluorobenzyl 2-
(4-Chlorphenyl)-2-methylpropyl ether 4-chloroneofyl chloride 8.53g, 3-
Phenoxy-4-fluorobenzyl alcohol
8.72g, 45% NaOH3.9g and 48g dimethyl sulfoxide were heated and stirred at 140°C for 3 hours. 45%
1.8 g of NaOH was added and the reaction was continued at the same temperature for an additional 4 hours. The reaction solution was discharged into 500 ml of water, extracted with benzene, and the benzene extract was washed with water and dried with Glauber's salt. The crude ether obtained by distilling off benzene under reduced pressure was separated and purified by column chromatography on 250 g of silica gel (developing solvent: toluene/n-hexane 1:1) to obtain the desired ether.
7.27 g (77% theoretical yield vs. consumed 4-chlorneofyl chloride) was obtained. n ²⁰ _D 1.5710 The infrared spectrum and NMR spectrum were consistent with the ether obtained in Synthesis Example 3. Synthesis Example 6 3-phenoxy-6-chlorobenzyl 2-
(4-chlorophenyl)-2-methylpropyl ether 2-(4-chlorophenyl)-2-methylpropyl alcohol 2.0 g, 3-phenoxy-6-chlorobenzyl bromide 3.5 g, 50% NaOH 20 g,
Toluethylbenzylammonium bromide 0.4
g was placed in a 50 ml separable flask and stirred at 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 subjected to column chromatography on 150 g of silica gel (developing solvent: toluene-
3.8 g (87% of theoretical yield) of the desired ether was obtained by purification using hexane (1:1). n ^19.5 _D 1.5854 ν ^film _nax 1500, 1480, 1275, 1260, 1215, 1110,
1020, 830cm ^-1 δ _ccl4 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-chlorophenyl)-2,3-dimethylbutyl ether Sodium hydride (60% in
Add 0.60g of 2-(4-
2.0 g of chlorophenyl-2-isopropyl alcohol/40% DMF-toluene 10 ml solution.
It was added dropwise over 20 minutes. After continuing to stir for 10 minutes, a solution of 3.5 g of 3-phenoxy-4-fluorobenzyl bromide/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 silica gel 120.
The product was purified by column chromatography (developing solvent: toluene-hexane 1:1) to obtain 2.8 g of the desired ether (72% of theoretical yield). n ^19.9 _D 1.5656 ν ^film _nax 1610, 1530, 1510, 1450, 1300, 1230,
1140, 1120, 1030cm ^-1 δ _ccl4 0.62 (d, 3H, J=6.8Hz), 0.85 (d, 3H,
J = 6.8Hz), 1.19 (S, 3H), 1.9~2.3 (m,
1H), 3.34 (d, 1H, J _AB = 8.8Hz) 3.53 (d, 1H, J _AB = 8.8Hz) AB type 4.30 (S, 2H), 6.7~7.4 (m, 12H) Below is the general formula of the starting materials. The method for producing [] will be explained in detail with reference to Synthesis Examples. Synthesis Example 8 It was synthesized according to the following order. (1) 10g of arylacetonitrile, 20g of KOH,
Methyl iodide (1.2 molar ratio to arylacetonitrile) was added dropwise to 20 g of H ₂ O and 2 g of triethylbenzylammonium bromide over 1 to 2 hours while maintaining the temperature at 80 to 90°C. then
10 g of KOH and 2 g of triethylbenzylammonium bromide were added, and at the same temperature, a desired alkyl halide (1.2 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. (2) The dialkyl form of arylacetonitrile synthesized in (1) was hydrolyzed with 50% H ₂ SO ₄ or water-soluble diethylene glycol-KOH at 130 to 150°C to obtain 2-aryl-2-alkylpropionic acid. Representative compounds are shown below. (R) _n R ₁ mp H CH ₃ - 75 to 76.5℃ 3-Cl CH ₃ - 66.5 to 67.5℃ 3,4-Cl ₂ CH 3 - 93.5 to 94.5℃ 4-CH _{3 CH 3 -} 80 to 81.5℃ 4 -Cl C ₂ H ₅ - 59~61.5℃ 4-OCH ₃ CH ₃ - 82.5~84℃ (3) Reducing the 2-aryl-2-alkylpropionic acid synthesized in (2) with lithium aluminum hydride in tetrahydrofuran. The desired 2-aryl-2-alkylpropyl alcohol was obtained. Synthesis Example 9 2-(4-chlorophenyl)-2-methylpropyl alcohol Synthesized according to the following sequence. (1) After adding 1.5 g of ferric chloride to 169 g of chlorobenzene, hydrochloric acid gas was blown in for 10 minutes. Then,
46g of tertiary butyl chloride at 30℃
(1 hour) and kept at 30°C for an additional 2 hours.
After washing with an aqueous sodium carbonate solution and water, the mixture was distilled under reduced pressure to obtain 25 g of 4-tert-butylchlorobenzene (113° C./28 mmHg). (2) After adding 25 g of 4-tert-butylchlorobenzene synthesized in (1), 20 g of sulfuryl chloride, and a catalytic amount of benzoyl peroxide, the temperature was raised, kept at 100°C for 1 hour, and then distilled under reduced pressure. 2-(4-chlorophenyl)-2-methyl-1
-chloro-propane 17.0g (121~123℃/10mm
Hg) was obtained. (3) Add 27 g of magnesium (turnings) and a small amount of iodine as a catalyst to 100 ml of dry tetrahydrofuran, and add 2-(4-chlorophenyl) under heating under reflux.
-2-Methyl-1-chloropropane 20.3g 30
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. Then, after adding a saturated ammonium chloride 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. Then, 2-(4
-chlorophenyl)-2-methylpropyl alcohol (13.3 g) was obtained. mp 46-48℃ Analysis result C ₁₀ H ₁₃ ClO Calculated value (%) C 65.04 H 7.10 Cl 19.20 Actual value (%) C 64.18 H 6.95 Cl 19.16 Synthesis example 10 2-(3,4-methylenedioxyphenyl )-2
-Methylpropyl alcohol Synthesized according to the following sequence. (1) To 100 ml of dry ether were added 27 g of magnesium (turnings) and a small amount of iodine as a catalyst, and 17 g of methyl iodide was slowly added dropwise. Refluxing was continued for 30 minutes after the completion of the dropwise addition. Next, 100 ml of benzene was added dropwise while increasing the temperature to replace the ether with benzene. While heating under reflux, 18.9 g of raw material nitrile was added dropwise. After further heating under reflux for 3 hours, 6N-
20 ml of HCl was added dropwise over 30 minutes. Then the temperature was raised to 7
The mixture was heated to reflux for an hour. 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 19.2 g of the desired 2-(3,4-methylenedioxyphenyl)-2-methyl-3-butanone. (2) 12.8 g of bromine was added dropwise to 7.4 g of sodium hydroxide, 35 ml of water, and 10 ml of dioxane at below 20°C. Then, the temperature was raised to 90°C, and 10 g of 2-(3,4-methylenedioxyphenyl)-2-methyl-3-butanone was slowly added dropwise thereto, followed by heating and stirring at 90 to 95°C for 2 hours. After cooling to room temperature, a predetermined amount of sodium bisulfite was added and extracted with toluene. The aqueous layer was acidified with concentrated hydrochloric acid and extracted with toluene. This toluene layer was washed with water, dried over Glauber's salt, and the toluene was distilled off under reduced pressure to obtain 7.5 g of the desired 2-(3,4-methylenedioxyphenyl)-2-methyl-propionic acid. (3) The 2-(3,4-methylenedioxyphenyl)-2-methyl-propionic 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. ν ^film _nax 3390, 1495, 1235, 1040cm ^-1 δ _ccl4 1.25 (S, 6H), 3.39 (S, 2H), 5.87 (S
,
2H), 6.6-6.9 (m, 3H) 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-methyl-2-pentene in 100 ml of acetonitrile, 10 g of 50% NaOH was added dropwise. Then blowing difluorolmethane (Freon-22) was started at a temperature of 60-70°C.
After about 60% of the required amount of reaction was injected (after about 20 minutes)
Then, 10 g of 50% KOH was added and the blowing was continued. 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, it was poured into 500 ml of water and extracted with toluene. After washing the toluene layer with water, it was dried over Glauber's salt, and the toluene was distilled off under reduced pressure.The resulting crude ether was washed with silica. The product was purified by column chromatography using 200 g of gel (developing solvent: toluene) to obtain 19.2 g of the desired 2,4-bis(4-difluoromethoxyphenyl)-4-methyl-2-pentene. Yield 77%. n ^20.4 _D 1.5285. (2) 8.0 g of 2,4-bis(4-difluoromethoxyphenyl)-4-methyl-2-pentene was dissolved in 100 ml of acetone, and 30 g of KMnO ₄ was added at 30°C. After stirring for 10 hours at 30℃, excess
To decompose KMnO ₄ , 20 ml of ethyl alcohol was added dropwise under cooling. After continuing to stir for 1 hour, the produced manganese dioxide was filtered,
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. A dilute NaOH aqueous solution was added to the toluene layer, and after shaking well, the layers were separated. The resulting aqueous layer was made acidic with concentrated hydrochloric acid, extracted with toluene, washed with water, and dried. When toluene is distilled off under reduced pressure, the target 2
4.2 g of -(4-difluoromethoxyphenyl)-2-methylpropionic acid was obtained. (mp.68.5~69.5℃). Yield 84%. δ _ccl4 1.58 (S, 6H), 6.42 (t, 1H, J = 75Hz) 7.03 (d, 2H, J _AB = 8.8Hz) 7.37 (d, 2H, J _AB = 8.8Hz) AB type 11.76 (broad s, 1H) ppm (3) Add a solution of 2.0 g of 2-(4-difluoromethoxyphenyl)-2-methylpropionic acid/10 ml of tetrahydrofuran to a mixture of 20 ml of tetrahydrofuran and 0.5 g of lithium aluminum hydride at 40°C.
It was dripped at. After the dropping was completed, the temperature was raised and refluxed for 30 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 formed 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-
1.8 g of difluoromethoxyphenyl)-2-methylpropyl alcohol was obtained. Yield 96%. ν ^film _nax 3360, 1510, 1380, 1220, 1185, 1130,
1040, 835 cm ^-1 Synthesis Example 12 2-(4-fluorophenyl)-2-methylbutyl alcohol Synthesized according to the following sequence. (1) 4-fluorotoluene 16.6g, NBS30.0g,
0.5g benzoyl peroxide, carbon tetrachloride
150 ml was charged into a 300 ml flask and refluxed for 2.0 hours. After cooling to room temperature, the precipitate formed was removed by filtration, and the CCL ₄ solution was washed with dilute alkali and water in that order, and dried with Glauber's salt. Carbon tetrachloride was distilled off under reduced pressure to obtain crude 4-fluorobenzyl bromide (28.8 g)
I got g. A solution of 28.8 g of the crude bromide obtained above in 30 ml of ethanol in 8.8 g of NaCN and 9.0 g of water at 70-80℃
(for 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. Under reduced pressure
Benzene was distilled off to obtain 13.2 g of crude 4-fluorobenzyl cyanide. ν ^film _nax 2270, 1615, 1520, 1430, 1240, 1170,
825 cm ^-1 . (2) Crude 4-fluorobenzyl cyanide obtained in (1)
12.8 g, 50% NaOH, 40 g, and 2 g of triethylbenzylammonium bromide were placed in a flask, and 14 g of methyl iodide was added dropwise with stirring (70 g).
°C, 15 min). After further keeping at 70°C for 30 minutes, it was cooled to room temperature and drained 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 to obtain 13.4 g of α-methyl-4-fluorobenzyl cyanide. A flask was charged with 7.0 g of α-methyl-4-fluorobenzyl cyanide, 15 g of KOH, 10 g of H ₂ O, and 2.0 g of triethylbenzylammonium bromide, and 10 ml of ethyl bromide was added dropwise at 80° C. over 1 hour with stirring. Then, it was kept at the same temperature for 2 hours. The subsequent operations are as described above. 7.9 g of crude α-ethyl-α-methyl-4-fluorobenzyl cyanide was obtained. Crude α-ethyl-α-methyl-4-fluorobenzyl cyanide 7.6 g, H ₂ O 20 ml, concentrated sulfuric acid 20
ml was placed in a flask and heated under reflux at 134-137°C for 5.5 hours. The mixture was cooled to room temperature and extracted with benzene. Benzene 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 diluted with concentrated hydrochloric acid, pH 4.6, 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 3.8 g of the desired 2-(4-fluorophenyl)-2-methylbutyric acid. δ _CDCl3 0.85 (t, 3H, J=7Hz), 1.55 (S,
3H), 1.8-2.3 (m, 2H), 7.0-7.6 (m,
4H), 11.3 (broad S, 1H) (3) A solution of 3.0 g of 2-(4-fluorophenyl)-2-methylbutyric acid/10 ml of tetrahydrofuran was added dropwise to a mixture of 20 ml of tetrahydrofuran and 0.5 g of lithium aluminum hydride at 40°C. did. After the dropping was completed, the temperature was raised and refluxed for 30 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 formed 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
2.6 g of -(4-fluorophenyl)-2-methylbutyl alcohol was obtained. n ²³ _D 1.5035 ν ^film _nax 3360, 1610, 1520, 1240, 1175, 1040,
840cm ^-1 Synthesis Example 13 2-(4-Methylthiophenyl)-2-methylpropyl alcohol Synthesized according to the following sequence. (1) Synthesis of 4-methylthiobenzyl chloride 18.2g of methylal was added to 1,2-dichloroethane.
61.4 g of anhydrous aluminum chloride was added to the solution while cooling with water. To this, 24.8 g of thioanisole was added dropwise at room temperature, and the mixture was stirred for 3 hours to react. After the reaction is complete, drain into water,
After adding concentrated hydrochloric acid to dissolve the solid matter, it was extracted with benzene, and the extract was washed with water, diluted sodium bicarbonate water, and water. After drying with Glauber's salt, the solvent was removed to obtain 30.7 g of an oily residue. (2) Synthesis of (4-methylthiophenyl)-acetonitrile Dissolve 10.5 g of soda cyanide in 12 g of water and heat to 60°C. To this was added dropwise 30.7 g of the oil obtained in (1) above dissolved in 35 ml of ethanol, and the mixture was refluxed for 4 hours to react. The residue was worked up 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). δ _ccl4 2.37 (S, 3H), 3.56 (S, 2H), 7.16 (S
,
4H) (3) Synthesis of 1-(4-methylthiophenyl)-1,1-dimethylacetonitrile From 13.1 g of (4-methylthiophenyl)-acetonitrile in the same manner as in (1) of Synthesis Example 10.
13.9g of the target product was obtained. δ _ccl4 1.66 (S, 6H), 2.45 (S, 3H), 7.2-7.6
(m, 4H) (4) Synthesis of 1-(4-methylthiophenyl)-1-methylpropionic acid 1-(4-methylthiophenyl)-
Add 3.8g of 1,1-dimethylacetonitrile,
The reaction was carried out at 130-140°C 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 brine, dried over sodium sulfate, and desolvated to obtain solid 1-(4-methylthiophenyl)-1-methylpropionic acid.
I got 1.9g. δ acetone _d6 1.54 (S, 6H), 2.43 (S, 3H),
7.0 to 7.5 (m, 4H) (5) Synthesis of 2-(4-methylthiophenyl)-1-methylpropyl alcohol Reduce with lithium aluminum hydride in the usual manner to produce 1-(4-methylthiophenyl)-1- 1.5g of desired alcohol from 1.9g of methylpropionic acid
I got it. δ _ccl4 1.26 (S, 6H), 2.39 (S, 3H), 3.38 (S
,
2H), 7.0 to 7.4 (m, 4H) Synthesis Example 14 Synthesis of 2-(4-chlorophenyl)-2-methylpropylthiol (1) Synthesis of 2-(4-chlorophenyl)-2-methylpropyl tosylate 2 Add 20 ml of pyridine to 10.0 g of -(4-chlorophenyl)-2-methylpropyl alcohol and 10.8 g of p-toluenesulfonyl chloride, and add 50 ml of pyridine.
The reaction was carried out at ~55°C for 1 hr. The reaction mixture was poured into 100 g of ice water, acidified with dilute hydrochloric acid, and extracted with benzene. After washing the benzene layer with saturated saline,
Dry with Glauber's salt and remove the solvent under reduced pressure to obtain 19.3g.
A white solid residue was obtained. Melting point 69-71.5℃ δ _ccl4 1.31 (S, 6H), 2.44 (S, 3H), 3.89 (S
,
2H), 7.13 (S, 4H), 7.18-7.60 [m, 4H
(AB TYpe)] ν ^KBr _nax 1595, 1480, 1355, 1175, 970, 825cm ^-1 (2) Synthesis of bis-[2-(4-chlorophenyl)-2methylpropyl]disulfide Tosylate 13.0 obtained in (1) g and sodium hydrogen sulfide
20.0g (70% product) and 100ml of 90% ethanol
The mixture was reacted for 3 hours under reflux while stirring. The reaction product was poured into water, extracted with benzene, and the benzene layer was washed with water and then dried with sodium sulfate.
Benzene was distilled off under reduced pressure to obtain 7.9 g of a liquid residue. This was separated by silica gel column chromatography using a mixed solvent of benzene-hexane (1:3), and 5.3 g (oil) of the target product was obtained.
I got it. ν ^film _nax 2950, 1500, 1410, 1395, 1380, 1120,
1105, 1020, 830, 755cm ^-1 δ _ccl4 1.31 (S, 6H), 2.81 (S, 2H), 7.18 (d
,
4H) Elemental analysis C H S Cl Calculated value % 60.17 6.01 16.06 17.76 Measured value % 59.06 6.07 16.55 17.56 (3) Synthesis of 2-(4-chlorophenyl)-2-methylpropylthiol 0.095 g of lithium aluminum hydride in 25 ml of dry ether and bis-[2-(4-chlorophenyl) dissolved in 10 ml of ether.
-2-Methylpropyl disulfide 1.0g
was added dropwise, and the mixture was reacted under reflux for 2 hours. After the reaction is complete, the reaction product is drained into water, 15% dilute sulfuric acid is added,
Extracted with benzene. The benzene layer was washed with saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 1.0 g of a liquid residue. ν ^film _nax 2965, 2570, 1495, 1405, 1390, 1370,
1105, 1020, 830cm ^-1 δ _ccl4 0.80 (t, 1H), 1.33 (S, 6H), 2.68 (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 than when the compounds shown in Table 1 are applied alone. That is, the composition of the present invention is effective against mercury, agricultural and horticultural forest pests that cause damage to field crops, cotton, forests, etc. (e.g., leafhoppers, planthoppers, beetles, rice beetles, rice weevils, rice weevils, stink bugs, aphids, green caterpillars, etc.). , armyworms, diamondback moths, cutworms, seed flies, scale beetles, scale insects, leafhoppers, spider mites, American white beetles, gypsy moths, bark beetles, nematodes, thrips, etc.), as well as storage pests such as brown weevils and cutworms, flies, Against a wide range of pests, including sanitary pests such as mosquitoes and cockroaches.
It has pesticidal efficacy at low concentrations. The second feature of the composition of the present invention is that it exhibits remarkable insecticidal and acaricidal effects even against insect pests that have already developed resistance to organophosphorus insecticides and acaricides and/or carbamate insecticides and acaricides. Moreover, it has characteristics that make it difficult to develop chemical resistance against various pests. In addition, the third feature is that the composition of the present invention has fast-acting properties that are not found in general organophosphorus insecticides and acaricides and carbamate insecticides and acaricides.
It is possible to make pests fall and turn over in a short time after spraying the chemical. Furthermore, the fourth feature is that it has low toxicity to fish and warm-blooded animals and has no risk of causing environmental pollution, making it an extremely ideal insecticide and acaricide. When actually applying the composition of the present invention, it is sufficiently effective even if the composition itself is diluted.
In order to make it easier to use as a pesticidal agent, it is common to mix various carriers into a preparation, dilute it as necessary, and apply it. In formulating the composition of the present invention, emulsions, emulsions,
For any dosage form such as wettable powders, powders, fine granules, granules, oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.), fogging agents, non-heated fumigants, poison baits, etc. It can be prepared and 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 BHT and BHA, bisphenol derivatives, A composition with stable effects can also be obtained by adding an appropriate amount of arylamines or benzophenone compounds such as phenyl α-naphthylamine, phenyl β-naphthylamine, and a condensate of phenetidine and acetone as a stabilizer. Further, for the purpose of obtaining a multipurpose agricultural chemical, 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. The composition ratio of the compound of the general formula [] and the carbamate insecticide and acaricide in the composition of the present invention is 99:1.
~1:99, preferably 1:9 to 1:1. When the composition of the present invention is formulated, the active ingredient concentration is 5 to 50% for emulsions, 0.3 to 3% for powders, 5 to 50% for wettable powders, and 0.5 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." “Carbamate insecticide/acaricide” in the formulation example
represents the compound described herein above. 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, 15 parts of carbamate insecticide/miticide, 10 parts of emulsifier Solpol SM-200 (trade name of Toho Chemical), and 70 parts of xylene are stirred and mixed to prepare an emulsion. Formulation Example 2 1 part of the compound shown in Table 1 and 3 parts of carbamate insecticide and acaricide were dissolved in acetone, and powder clay 96
After adding 50% of the mixture, stir to evaporate the acetone and make a powder. Formulation example 3 Add 15 parts of carbamate insecticide and acaricide to 5 parts of the compound shown in Table 1, and add emulsifier Solpol 355TLL.
(Toho Chemical brand name) Add 5 parts, stir well,
Add 75 parts of diatomaceous earth (300 mesh) and thoroughly stir and mix in a Raikai machine to prepare a wettable powder. Formulation Example 4 Add 5 parts of a carbamate insecticide and acaricide to 3 parts of the compound in Table 1, add 88 parts of clay, and Toyolignin CT.
(Toyobo registered trade name) Add 4 parts and mix well.
After adding water and stirring, the mixture is granulated using a granulator.
Dry to make granules. Formulation Example 5 Add 5 parts of a carbamate insecticide or acaricide to 1 part of the compound shown in Table 1, dissolve in white kerosene, etc., and make an oil solution to make 100 parts. Formulation example 6 Add carbamate insecticide to 0.2g of the compound in Table 1.
Add 0.2 g of acaricide, 0.9 g of synergist, and 0.3 g of BHT, dissolve in 20 ml of methanol, and prepare each carrier for mosquito coil (a mixture of tab powder, lees powder, and wood flour in a ratio of 3:5:1). ) 99.4g and evaporate the methanol, add 150ml of water, mix well, mold and dry to make a mosquito coil. Formulation example 7 0.1g of the compound in Table 1, carbamate insecticide
Add 0.2g of BHT to 0.1g of acaricide, 1.0g of synergist,
Dissolve it in chloroform, adsorb it on a 0.3 cm thick paper, and heat it on an electric heating plate to prepare a fiber fumigation composition. Formulation example 8 0.1 part of the compound in Table 1, carbamate insecticide
Acaricide 0.1 part, synergist 0.3 part, xylol 7 parts,
Mix and dissolve 7.5 parts of deodorized kerosene. Fill the aerosol container with this and attach the valve. 80 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to form an aerosol. Formulation example 9 0.1 part of the compound in Table 1, carbamate insecticide
Acaricide 0.1 part, synergist 0.3 part, deodorized kerosene 11.5 parts,
Mix with 1 part of emulsifier Atmos 300 (registered trade name of Atlas Chemical Company), add 50 parts of pure water and emulsify. This is filled into an aerosol container with 37 parts of a 3:1 mixture of bromide and deodorized propane to form a water-based aerosol. Next, we will list specific names of insect pests to which the insecticide and acaricide of the present invention can be applied [scientific name - (Japanese name)]. 1 Hemiptera Nephotettix cincticeps Uhler Sogatella furcifera Horvath Nilaparvata lugens Sta゜l Laodelphax striatellus Falle′n Eurydema rugosum Motschulsky Eysarcoris parvus Uhler Halyomorphamista Uhler Lagynotomus elongatus Dallas Nezara viridula Linne′ Cletus trigonus Thunberg Stephanitis nashi Esaki et Takeya Stephanitis pyrioides Scott Psylla pyrisuga Fo¨rster ) Psylla mali Schmidberger Aleurolobus taonabae Kuwana Dialeurodes citri Ashmead Trialeurodes vaporraiorum Westwood Aphis gossypii Glover Brevicoryne brassicae Linn′e Myzus persicae Sulzer ( Momo Rhopalosiphum maidis Fitch Icerya purchasi Maskell Planococcus citri Risso Unaspis yanonensis Kuwana 2 Lepidoptera Canephora asiatica Staudinger Spulerina astaurcta Meyrick (Nashihoso moth) Phyllomycter ringoneella Matsumura
(Plutella xylostella Linn′e) Promalactis inopisema Butler (Boll moth) Adoxophyes orana Fischer von
Ro¨slerstamn Bactra furfura′na Haworth Leguminivora glycinivorella Matsumura
Cnaphalocrocis medinalis Guen′ee Etiella zinckenella treitschke Ostrinia furnacalis Guen′ee Pleuroptya derogata Fabricus Hyphantria cunea Drury Abraxas miranda Butler ) Lymantria dispar japonica Motschulsky
(Gypsy moth) Phalera fiavescens Bremer et Gray (Gypsy moth) Agrotis segetum Denis et Schiffer
mu¨ller Helicoverpa armigera Hu¨bner Pseudaletia separata Walker Mamestra brassicae Linn′e Plusia nigrisigna Walker Spodoptera litura Fablicius Parnara guttata Bremer et Gray Pieris rapae crucivora Boisduval Chilo suppressalis Walker 3 Coleoptera Melanotus fortnumi Cande'ze Anthrenus verbasci Lunn'e Tenebroides mauritanicus Linn'e Lyctus brunneus Stephens Henosepilachna vigintioctopunctata
Fablicius Monochamus alternatus Hope Xylotrechus pyrrhoderus Bates Aulacophora femoralis Motschlusky Oulema oryzae Kuwayama Phyllotreta striolata Fablicus Callosobruchus chinensis Linn'e (Azuki bean weevil) Echinocnemis Squameus Billberg (Momochi Yotsukiri Muarushi) Anomala Cuprea Hope (Douganebui) Popillia Japonica Newman (Mamekogane) 4 Hymenoptera Athalia rosae japonensis Rohwer Arge similis Vollenhoven Arge pagana Panzer 5 Piptera Tipula aino Alexander Culex pipiens fatigans Wiedemann Aedes aegypti Linn'e (Netsu Taishimaka) Asphondylia SP. S CUCURBITAE COQUILLETTTTTT (Inecarabae) Agromyza ORYZAE MUNAKATA 6 Siphonaptera Pulex irritans Linn'e (Human flea) Xenopsylla cheopis Rothschild Ctenocephalides Canis Curtis 7 Thysanoptera Scirtothrips dorsalis Hood Thrips tabaci Lindeman Thrips Chloethrips oryzae Williams 8 Anoplura Pediculus humanus corporis De Geer Phthirus pubus Linn'e Haematopinus eurysternus Nitzsh 9 Psocoptera Trogium pulsatsrium Lunn'e Tatebug ) Liposcelis bostrychophilus Badonnel 10 Orthoptera Gryllotalpa africana palisot de Beauvois
Locusta migratoria danica Linn′e Oxya yezoensis Shiraki 11 Dictyoptera Blattella germanica Linn′e Periplaneta fuliginosa Serville 12 Acarina Boophilus microplus Canestrini Polyphagotarsonemus latus Banks Panonychus citri McGregor Tetranychus cinnabarinus Boisduval Tetranychus urticae Koch Rhizoglyphus echinophus Fumouze et
Robin Next, the effect of the composition of the present invention as an insecticide/acaricide will be explained in detail by giving test examples. Test Example 1 Effect on susceptible Paddy planthoppers Young paddy rice seedlings (2-3 true leaves) were grown hydroponically in pots with a diameter of 5 cm. The chemical solution was sprayed at 3 ml/pot. After air-drying, the seedlings were covered with a wire mesh cylinder, 10 male adults of the susceptible brown planthopper (from Chigasaki) were released per pot, and the seedlings were left in a room at 25°C. 24 hours after the treatment, the number of live and dead insects was investigated, and the mortality rate was calculated. The results are the average values of three consecutive runs and are shown in Table 2 below. As a result, when both the test compound (indicated by the compound number in Table 1) and the carbamate-based insecticide were applied in combination, almost 100% insect mortality was achieved, and an excellent synergistic effect was observed. Test Example 2 Effect on resistant leafhopper Rice seedlings (2 to 3 true leaves) were hydroponically cultivated in pots with a diameter of 5 cm, and the concentration of each test chemical was 10 ppm using the method shown in Formulation Example 1. Each pot was treated with 3 ml of the chemical solution using a sprayer. After air-drying, the seedlings were covered with a wire mesh cylinder, 10 adult male resistant leafhoppers (native to Nakagawa) were released into each pot, and left in a room at 25°C. 24 hours after treatment, the number of live and dead insects was investigated and the mortality rate was calculated. The results are shown in Table 3 below as the average value of three series. A remarkable synergistic effect was also observed in this case. The method described in this specification was conducted in the same manner as in Test Examples 1 and 2.
As a result of testing mixtures of carbamate-based insecticides and acaricides other than MTMC, NAC, and NIPC and the compounds listed in Table 1, almost the same insecticidal and acaricidal effects as in Test Examples 1 and 2 were obtained. (See Tables 4 and 5)

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Claims (1)

[Claims] 1. General formula [In the formula, Ar is a lower alkyl-substituted naphthyl group, an unsubstituted phenyl group, a halogen atom at the 4-position, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a cyano group, or a nitro group. a phenyl group substituted with, a halogen atom at the 3-position in addition to the 4-position,
A phenyl group substituted with a lower alkyl group or a lower alkoxy group or a phenyl group substituted with a methylenedioxy group, R ₁ is a methyl group or ethyl group, R ₂ is a methyl, ethyl group or isopropyl group, R ₃ is a hydrogen atom or a halogen atom,
R ₄ represents a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 2 carbon atoms, or a lower alkoxy group having 1 to 2 carbon atoms, respectively. X represents an oxygen atom or a sulfur atom. ] 2-
One or more arylethyl ether or thioether derivatives and 1-naphthylmethyl carbamate (NAC), m-tolylmethyl carbamate (MTMC), o-cumenylmethyl carbamate (MIPC), o-sec-butylphenylmethyl A carbamate-based insecticide and acaricide consisting of carbamate (BCMC), o-isopropoxyphenylmethyl carbamate (PHC), 3,4-xylyl methyl carbamate (MPMC), and 3,5-xylyl methyl carbamate (XMC). An insecticidal and acaricidal composition containing one or more of these.