JPH0360810B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel 2-arylpropyl ether derivatives and thioether derivatives, methods for producing the same, and low-toxicity insecticides and acaricides containing the compounds. More specifically, one aspect of the present invention is the general formula [] [Wherein, Ar is an unsubstituted or lower alkyl-substituted naphthyl group, or an unsubstituted or halogen atom,
Lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkenyl group, lower haloalkenyl group, lower alkenyloxy group, lower haloalkenyloxy group, lower alkynyl group, Represents a phenyl group substituted with a lower alkynyloxy group, a lower alkoxy lower alkyl group, a lower acyl group, a lower alkoxycarbonyl group, a cyano group, a nitro group or a methylenedioxy group, R represents a methyl group or an ethyl group, and Y represents an oxygen atom or a sulfur atom, and B is a general formula [] or a general formula [] (In the formula [], Z represents an oxygen atom, a sulfur atom, a carbonyl group, or a methylene group, and R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. n represents an integer from 1 to 5. .Herein, when n is 2 or more, R ¹ may be the same or different. However, cases where the general formula [] is 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether or the general formula [] are not included. (In the formula [], R represents the above meaning, R ²
represents a halogen atom or a lower alkyl group,
m represents 1 or 2. 2-arylpropyl ether derivatives and thioether derivatives represented by R ² (when m is 2, R2 may be the same or different). One of the aspects of the present invention is to convert a compound represented by the general formula [] into a compound represented by the general formula []

[Group A = halogen atom]

(3)H ₃ ⁺ O Reference J.Am.Chem.Soc., 65 , 1469 (1943) [] HaSH ------→ EtOH [] [Group A=SH] [Group A=Halogen atom] Reference Chem.Ber., 94 , 2609 (1961) [] [Group A=OH or
SH】. In addition, the alcohol of the general formula [] [in the formula, when group A is a hydroxyl group] is Helvetica
It can also be produced by the method described in Chimica Acta, 54 , 868 (1971). The metal alcoholate or metal thioalcoholate of the general formula [] [in which the group A represents a Y-M group (Y represents the above meaning) and M is not a hydrogen atom] can be prepared by a conventional method, for example, sodium hydride. Reacting a metal hydride with an alcohol or thiol of the general formula [ ] [wherein A represents a Y-M group (Y represents the above meaning) and M is a hydrogen atom]. can be easily obtained. Alcohols of the general formula [] [where radical D is a hydroxyl group] are known as alcohol components of synthetic pyrethroids or are prepared by known methods described in the literature. General formula []
[In the formula, when group D represents Y--H and Y represents a sulfur atom] the thiol is produced from the corresponding alcohol by a conventional method. Next, the method for producing 2-arylpropyl ether derivatives and thioether derivatives of the present invention will be described in more detail with reference to synthesis examples. Synthesis Example 1 (Etherification method A) 3-(4-methoxyphenoxy)benzyl 2-
(4-Methylphenyl)-2-methylpropyl ether Add 0.90 g of sodium hydride (60% in oil) to 20 ml of dry acetonitrile, then (2-(4
-Methylphenyl)-2-methylpropyl alcohol (2.5 g/10 ml acetonitrile solution) was added dropwise at 50°C. After heating under reflux for 30 minutes, a solution of 5.3 g of 3-(4-methoxyphenoxy)benzyl bromide in 10 ml of acetonitrile was added dropwise over 10 minutes.
The mixture was heated to reflux for an hour. After cooling to room temperature, the mixture was extracted with toluene which was poured into water. 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 using 150 g of silica gel (developing solvent: toluene/n-hexane 1:1) to obtain 3.4 g of the desired ether (theoretical yield 59%). ) was obtained. n ²⁰ _D 1.5707 ν ^film _nax 1590, 1510, 1490, 1245, 1215, 1105,
1040, 815cm ^-1 δ ^ccl4 _TMS (ppm) 1.30 (s, 6H), 2.28 (s, 3H),
3.35 (s, 2H), 3.75 (s, 3H), 4.38 (s,
2H), 6.7-7.3 (m, 12H) Elemental analysis results C ₂₅ H ₂₈ O ₃ Calculated value (%) C; 79.75, H; 7.50 Actual value (%) C; 79.99, H; 7.48 Synthesis Example 2 (Ether Chemical method B) 3-(4-fluorophenoxy)benzyl 2-
(3,4-Dichlorophenyl)-2-methylpropyl ether Sodium hydride (60% in
Add 0.63g of 2-(3,
4-dichlorophenyl)-2-methylpropyl alcohol 2.3g/25% DMF-toluene 10ml solution
It was added dropwise over 15 minutes. After continuing to stir for 10 minutes, a solution of 3.5 g of 3-(4-fluorophenoxy)benzyl bromide/10 ml of toluene was added dropwise over 20 minutes. Furthermore, after heating under reflux for 1 hour, the mixture was cooled to room temperature and discharged into water. After extraction with toluene and washing the toluene extract with water, it was dried with Glauber's salt. The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography using 100 g of silica gel (developing solvent: toluene/n-hexane 1:1) to obtain 3.1 g of the desired purified ether (theoretical yield: 74 %) was obtained. n ²⁰ _D 1.5732 ν ^film _nax 1590, 1505, 1490, 1265, 1205, 1100,
1035, 695cm ^-1 δ ^ccl4 _TMS (ppm) 1.30 (s, 6H), 3.34 (s, 2H),
4.38 (s, 2H), 6.7-7.4 (m, 11H) Elemental analysis result C ₂₃ H ₂₁ Cl ₂ FO ₂ Calculated value (%) C; 69.09, H; 5.29, Cl;
8.87F; 4.75 Actual value (%) C; 68.88, H; 5.34, Cl;
8.75F; 4.57 Synthesis Example 3 (Etherification Method C) 3-(4-methylphenoxy)benzyl 2-(4
-chlorophenyl)-2-methylpropyl ether 15.0 g of 50% NaOH aqueous solution, 6.0 g of 2-(4-chlorophenyl)-2-methylpropyl alcohol,
8.1 g of 3-(4-methylphenoxy)benzyl chloride 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 on 250 g of silica gel (developing solvent: toluene/n-hexane 1:1) to obtain the desired ether. 9.9g (theoretical yield 80%)
I got it. n ²⁰ _D 1.5741 ν ^film _nax 1595, 1510, 1455, 1260, 1215, 1110,
1015, 830, 695 cm ^-1 δ ^ccl4 _TMS (ppm) 1.29 (s, 6H), 2.31 (s, 3H),
3.32 (s, 2H), 4.35 (s, 2H), 6.7~7.3
(m, 12H) Elemental analysis results C ₂₄ H ₂₅ ClO ₂ Calculated value (%) C; 75.68, H; 6.61, Cl; 9.31 Actual value (%) C; 75.86, H; 6.42, Cl; 9.22 Synthesis Example 4 (Etherification method D) 3-(4-fluorophenoxy)benzyl 2-
(4-Fluorophenyl)-2-ethylpropyl ether 20 ml of toluene, 2 ml of concentrated sulfuric acid, 2.7 g of 3-(4-fluorophenoxy)benzyl alcohol, 2-
2.3 g of (4-fluorophenyl)-2-ethylpropyl alcohol was added and heated under reflux for 6 hours (produced water was removed from the system 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 subjected to column chromatography on 100 g of silica gel (developing solvent: toluene/n
-hexane 1:1) to obtain 2.2 g (theoretical yield: 46%) of the desired ether. n ²⁰ _D 1.5478 ν ^film _nax 1585, 1505, 1230, 1195, 1165, 1100,
830, 780, 690cm ^-1 δ ^ccl4 _TMS (ppm) 0.65 (t, J=7.5Hz, 3H), 1.28
(s, 3H), 1.5-1.9 (m, 2H), 3.37 (s,
2H), 4.35 (s, 2H), 6.7-7.3 (m, 12H) Elemental analysis result C ₂₄ H ₂₄ F ₂ O ₂ Calculated value (%) C; 75.37, H; 6.32, F: 9.94 Actual value (%) C; 75.54, H; 6.21, F; 10.01 Synthesis Example 5 (Etherification Method E) 3-Phenoxybenzyl 2-(4-difluoromethoxyphenyl)-2-methylpropyl ether 2-(4-difluoromethoxy phenyl)-2-
Methylpropyl alcohol 2.0g, 3-phenoxybenzyl chloride 2.0g, 50% NaOH 20g,
Triethylbenzylammonium bromide 0.3
The mixture of g was stirred at 50°C for 2 hours. After adding water and benzyl and shaking well, the liquid was separated. The benzene layer was washed with water and dried with sodium sulfate. The crude ether obtained by distilling off benzene under reduced pressure was purified by column chromatography using 130 g of silica gel (developing solvent: toluene/hexane 2:3) to obtain 3.0 g of the desired ether (theoretical yield 81%). Ta. n ^20.5 _D 1.5490 ν ^film _nax 1580, 1485, 1380, 1250, 1215, 1130,
1040, 690cm ^-1 δ ^ccl4 _TMS (ppm) 1.32 (s, 6H), 3.36 (s, 2H),
4.21 (s, 2H), 6.38 (t, J=75Hz, 1H),
6.8-7.4 (m, 13H) Synthesis Example 6 3-(4-bromophenoxy)benzyl 2-(4
-fluorophenyl)-2-ethylpropyl ether Sodium hydride (60% in
Add 0.60g of 2-(4-
A solution of 2.0 g (fluorophenyl)-2-ethylpropyl alcohol/10 ml of 40% DMF-toluene was added dropwise over 20 minutes. After continuing to stir for 10 minutes,
A solution of 4.0 g of 3-(4-bromophenoxy)benzyl 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 off toluene under reduced pressure was subjected to column chromatography on 100 g of silica gel (developing solvent: toluene/
The desired ether (3.7 g, theoretical yield: 76%) was obtained by purification using hexane (1:1). n ^20.2 _D 1.5778 ν ^film _nax 1605, 1580, 1510, 1485, 1250, 1165,
1100, 1070, 1010, 830cm ^-1 δ ^ccl4 _TMS (ppm) 0.67 (t, J=7.2Hz, 3H), 1.30
(s, 3H), 1.5-1.9 (m, 2H), 3.39 (s,
2H), 4.39 (s, 2H), 6.7-7.5 (m, 12H) Synthesis Example 7 3-Phenoxybenzyl 2-(3,4-methylenedioxyphenyl)-2-methylpropyl ether 2-( 3,4-methylenedioxyphenyl)-2
- It was carried out according to Synthesis Example 2 using 0.4 g of methylpropyl alcohol. n ^20.7 _D 1.5839 ν ^film _nax 1590, 1490, 1255, 1105, 1045, 940cm ^-1 δ ^ccl4 _TMS (ppm) 1.28 (s, 6H), 3.32 (s, 2H),
4.41 (s, 2H), 5.82 (s, 2H), 6.5~7.4
(m, 12H) Synthesis Example 8 (Etherification Method F) 3-(4-methoxyphenoxy)benzyl 2-
(3,4-dichlorophenyl)-2-methylpropyl ether 3,4-dichloroneofyl chloride 9.98
g, 4-methoxyphenoxybenzyl alcohol
9.67 g of 45% caseizoda and 48 g of dimethyl sulfoxide were heated and stirred at 140° C. for 3 hours.
1.8 g of 45% caustic soda was added, and the reaction was continued at the same temperature for an additional 4 hours. The reaction solution was drained into water, extracted with benzene, and the benzene extract was washed with water.
Dried with Glauber's salt. The crude ether obtained by distilling off benzene under reduced pressure was separated and purified by column chromatography using 250 g of silica gel (developing solvent: toluene/n-hexane 1:1) to obtain 3.34 g of the desired ether (theoretical yield 78% vs. consumption of 3,4-dichloroneofyl chloride) was obtained. n ²⁰ _D 1.5830 ν ^film _nax 1590, 1510, 1490, 1250, 1220, 1110,
1040, 840cm ^-1 δ ^ccl4 _TMS (ppm) 1.30 (s, 6H), 3.34 (s, 2H),
3.76 (s, 3H), 4.38 (s, 2H), 6.7~7.5
(m, 11H) Synthesis Example 9 3-Phenoxybenzyl 2-(4-methylthiophenyl)-2-methylpropyl ether It was carried out according to Synthesis Example 2. n ^19.8 _D 1.5921 ν ^film _nax 2920, 1580, 1490, 1250, 1215, 1100,
815, 690cm ^-1 δ ^ccl4 _TMS (ppm) 1.31 (s, 6H), 2.37 (s, 3H),
3.36 (s, 2H), 4.38 (s, 2H), 6.6-7.4
(m, 13H) Synthesis Example 10 3-Phenoxybenzyl 2-(4-chlorophenyl)-2-methylpropylthioether It was carried out according to Synthesis Example 2. n ^19.7 _D 1.6074 ν ^film _nax 1595, 1505, 1495, 1460, 1265, 1225,
1175, 1110, 1025, 965, 835 cm ^-1 δ ^ccl4 _TMS (ppm) 1.30 (s, 6H), 2.53 (s, 2H),
3.29 (s, 2H), 6.83-7.22 (m, 13H) Typical compounds of the present invention are described as follows.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] The starting materials [] and the production method of [] will be explained in detail below using reference synthesis examples. Reference synthesis example 1

Synthesis of [Formula] Synthesis was performed according to the following order. (1) 10g of arylacetonitrile, 20g of KOH,
Methyl iodide (1.2 molar ratio relative to arylacetonitrile) was added dropwise to 20 g of water and 2 g of triethylbenzylammonium bromide while maintaining the temperature at 80°C to 90°C over 1 to 2 hours. Then KOH10
g, 2 g of triethylbenzylammonium bromide was added, and the desired alkyl halide (relative to arylacetonitrile) was added at the same temperature.
1.2 molar ratio) 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.

[Table] (3) The 2-aryl-2-alkylpropionic acid synthesized in (2) was reduced with lithium aluminum hydride in tetrahydrofuran to obtain the desired 2-aryl-2-alkylpropyl alcohol. Reference Synthesis Example 2 2-(4-chlorophenyl)-2-methylpropyl alcohol Synthesized according to the following order. (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
hr) and kept at 30°C for an additional 2 hours. After washing with an aqueous sodium carbonate solution and water, distillation under reduced pressure yields 4-tert-butylchlorobenzene25.
g (113°C/28mmHg). (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
-Chloropropane 17.0g (121~123℃/10mm
Hg) was obtained. (3) Add 2.7 g of magnesium (turnings) and a small amount of iodine as a catalyst to 100 ml of dry tetrahydrofuran, and add 20.3 g of 2-(4-chlorophenyl)-2-methyl-1-chloropropane under reflux.
was added dropwise over 30 minutes, and heating and refluxing was continued for 10 hours.
After cooling to room temperature, oxygen gas was blown in for 1 hour. Next, after adding a saturated aqueous ammonium chloride solution, most of the tetrahydrofuran was distilled off under reduced pressure, extracted with toluene, and the toluene was distilled off under reduced pressure to obtain crude alcohol. Next, it is recrystallized from cold hexane to obtain the desired 2-
13.3 g of (4-chlorophenyl)-2-methylpropyl alcohol was obtained. mp46～48℃ Elemental analysis results 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 Reference synthesis example 3 2 -(3,4-methylenedioxyphenyl)-2
-Methylpropyl alcohol Synthesized according to the following sequence. Magnesium (turnings) in 100ml of dry ether
2.7g of iodine was added as a catalyst, and 17g of methyl iodide was slowly added dropwise. 30 minutes after completion of dripping
Heating was continued at reflux for a minute. Next, 100 ml of benzene was added dropwise while increasing the temperature to replace ether with benzene. While heating under reflux, 18.9 g of the raw material nitrile was added dropwise. Furthermore, after heating under reflux for 3 hours, 6N-
20 ml of HCl 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 sodium sulfate. Benzene was distilled off under reduced pressure to obtain the desired 2-(3,4-methylenedioxyphenyl)-2-methyl-3-butanone 19.2
I got g. ν ^film _nax 2970, 2890, 1720, 1495, 1250, 1045,
940, 820cm ^-1 δ ^ccl4 _TMS (ppm) 1.38 (s, 6H), 1.85 (s, 3H),
5.91 (s, 2H), 6.67 (s, 3H) (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 a temperature 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. δ ^ccl4 _TMS (ppm) 1.61 (s, 6H), 6.03 (s, 2H),
7.04 (s, 3H) (3) The 2-(3,4-methylenedioxyphenyl)-2-methylpropionic 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, 2960, 1495, 1235, 1040, 940, 810
cm ^-1 δ ^ccl4 _TMS (ppm) 1.25 (s, 6H), 3.39 (s, 2H),
5.87 (s, 2H), 6.6-6.9 (m, 3H) Reference synthesis example 4 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 difluorochloromethane (Freon-22) was started at a temperature of 60-70°C. When about 60% of the amount required for the reaction had been blown into the reactor (after about 20 minutes), 10 g of 50% KOH was additionally charged, 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. The toluene layer was washed with water, dried with Glauber's salt, and the toluene was distilled off under reduced pressure. The resulting crude ether was purified by column chromatography using 200 g of silica gel (developing solvent: toluene) to obtain the desired 2,4-bis. 19.2 g of (4-difluoromethoxyphenyl)-4-methyl-2-pentene was obtained. 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 _TMS (ppm) 1.58 (s, 6H), 6.42 (t, J=7.
Five
Hz, 1H), 7.03 (d, J _AB = 8.8Hz, 2H) 7.37
(d, J _AB = 8.8Hz, 2H) 11.76 (broad s,
1H) (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 dropwise addition was completed, the temperature was raised and the mixture was heated under reflux 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 generated precipitate was removed by filtration, and tetrahydrofuran was distilled off under reduced pressure. Extraction was performed with benzene, and the benzene layer was washed with water and dried over Glauber's salt. Benzene was distilled off under reduced pressure to obtain the desired 2-(4-
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 Reference Synthesis Example 5 2-(4-fluorophenyl)-2-ethylpropyl alcohol Synthesized according to the following order. (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 and removing the generated precipitate by filtration, 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.
28.8g was obtained. A solution of 28.8 g of the crude bromide obtained above/30 ml of ethanol in 8.8 g of NaCN and 9.0 g of water was added at 70 to 80 g.
It was added dropwise (30 minutes) at °C. The mixture was then kept at 80°C for 5.0 hours, cooled to room temperature, and discharged into water. Celite and benzene were added to this and stirred, and then Celite was removed by filtration. After separation, the benzene layer was washed with water and dried over anhydrous sodium sulfate. Benzene was distilled off under reduced pressure to obtain 13.2 g of crude 4-fluorobenzyl cyanide. ν ^film _nax 2270, 1615, 1520, 1430, 1240, 1170,
825cm ^-1 (2) Crude 4-fluorobenzyldianide 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 water, 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, at the same temperature for 2
It kept time. 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 7.6g, water 20ml, concentrated sulfuric acid 20ml
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. 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. Next, 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 3.8 g of the desired 2-(4-fluorophenyl)-2-ethylpropionic acid. δ ^ccl _3TMS (ppm) 0.85 (t, J=7Hz, 3H), 1.55
(s, 3H), 1.8~2.3 (m, 2H), 7.0~7.6
(m, 4H), 11.3 (broad s, 1H) (3) Add a solution of 3.0 g of 2-(4-fluorophenyl)-2-methylbutyric acid/10 ml of tetrahydrofuran to a mixture of 20 ml of tetrahydrofuran and 0.5 g of lithium aluminum hydride for 40 minutes. It was added dropwise at ℃. After the dropwise addition was completed, the temperature was raised and the mixture was heated under reflux 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 generated precipitate was removed by filtration, and tetrahydrofuran was distilled off under reduced pressure. Extraction was performed with benzene, and the benzene layer was washed with water and dried over Glauber's salt. Benzene was distilled off under reduced pressure to obtain the desired 2
2.6 g of -(4-fluorophenyl)-2-ethylpropyl alcohol was obtained. n ²³ _D 1.5035 ν ^film _nax 3360, 1610, 1520, 1240, 1175, 1040,
840cm ^-1 Reference Synthesis Example 6 2-(4-Methylthiophenyl)-2-methylpropyl alcohol Synthesized according to the following order. (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 was completed, the mixture was poured into water, concentrated hydrochloric acid was added to dissolve the solids, and then extracted with benzene. The extract was washed with water, 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. The above (1) dissolved in 35 ml of ethanol
30.7 g of the oil obtained above was added dropwise, and the mixture was heated under reflux for 4 hours to react. After post-treatment in a conventional manner, the residue was separated by column chromatography using benzene as a developing solvent to obtain 14.7 g of (4-methylthiophenyl)acetonitrile (oil). ν ^film _nax 2260, 1500, 1420, 1105, 800cm ^-1 δ ^ccl4 _TMS (ppm) 2.37 (s, 3H), 3.56 (s, 2H),
7.16 (s, 4H) (3) Synthesis of 1-(4-methylthiophenyl)-1,1-dimethylacetonitrile Synthesis of (4-methylthiophenyl)-acetonitrile 13.1 in the same manner as in (1) of Reference Synthesis Example 1 from g
13.9g of the target product was obtained. δ ^ccl4 _TMS (ppm) 1.66 (s, 6H), 2.45 (s, 3H),
7.2
~7.6 (m, 4H) (4) Synthesis of 1-(4-methylthiophenyl)-1-methylpropionic acid Add 1-(4-methylthiophenyl)- to 5.0 g of caustic potash, 5 g of water, and 20 ml of diethylene glycol.
Add 3.8g of 1,1-dimethylacetonitrile,
Heated at 130-140°C for 7 hours. After the reaction was completed, the mixture was cooled, poured 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 Glauber's salt, and the solvent was removed to obtain 1.9 g of solid 1-(4-methylthiophenyl)-1-methylpropionic acid. δ Acetone ^d _6TMS (ppm) 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) 1.5 g of the target alcohol was obtained from 1.9 g of -1-methylpropionic acid. δ ^ccl4 _TMS (ppm) 1.26 (s, 6H), 2.39 (s, 3H),
3.38 (s, 2H), 7.0-7.4 (m, 4H) Reference synthesis example 7 Synthesis of 2-(4-chlorophenyl)-2-methylpropylthiol (1) 2-(4-chlorophenyl)-2-methylpropyl Synthesis of tosylate Add 10.0 g of 2-(4-chlorophenyl)-2-methylpropyl alcohol and 10.8 g of p-toluenesulfonyl chloride to 20 ml of pyridine, and heat at 50-55°C.
It reacted for 1 hour. Drain the reactants into 100g of ice water,
The mixture was acidified with dilute hydrochloric acid and extracted with benzene. The benzene layer was washed with saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 19.3 g of a white solid residue. Melting point 69-71.5℃ ν ^KBr _nax 1595, 1480, 1355, 1175, 970, 825cm ^-1 δ ^ccl4 _TMS (ppm) 1.31 (s, 6H), 2.44 (s, 3H),
3.89 (s, 2H), 7.13 (s, 4H), 7.18~7.60
(m, 4H) (2) Synthesis of bis-[2-(4-chlorophenyl)-2-methylpropyl]disulfide 13.0 g of tosylate obtained in (1) and 20.0 g of sodium hydrogen sulfide
(70% product) and 100 ml of 90% ethanol were heated under reflux for 3 hours while stirring. The reaction product was discharged into water, extracted with benzene, and the benzene layer was washed with water and then dried with Glauber's salt. Benzene was distilled off under reduced pressure to obtain 7.9 g of a liquid residue. This was separated by silica gel column chromatography using a mixed solvent of benzene-hexane (1:3) to obtain 5.3 g (oil) of the target product. ν ^film _nax 2950, 1500, 1410, 1395, 1380, 1120,
1105, 1020, 830, 755 cm ^-1 δ ^ccl4 _TMS (ppm) 1.31 (s, 6H×2), 2.81 (s, 2H
×
2), 7.18 (d, 4H×2) Elemental analysis results 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) 2-(4-chlorophenyl)-2-methyl Synthesis of propylthiol Suspend 0.095 g of lithium aluminum hydride in 25 ml of dry ether, add bis-[2-(4-chlorophenyl)-2-
Add 1.0 g of methylpropyl disulfide dropwise,
The reaction was carried out 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 solvent was distilled off under reduced pressure to obtain 1.0 g of liquid residue.
I got it. ν ^film _nax 2965, 2570, 1495, 1405, 1390, 1370,
1105, 1020, 830cm ^-1 δ ^ccl4 _TMS (ppm) 0.80 (t, 1H), 1.33 (s, 6H),
2.68 (d, 2H), 7.23 (s, 4H) List the names of specific pests to which the insecticide and acaricide of the present invention can be applied [scientific name - (Japanese name) - English name]. 1 Hemiptera Nephotettix cincticeps Uhler Green rice leafhopper Sogata furcifera Torvwth White-backed rice plant hopper Nilaparvata lugens Stul Brown rice planthopper Laodelphax striatellus Fallvn Small brown planthopper Eurydema rugosum Motschulsky ( Cabbage bug Eysarcoris parvus Uhler Whitespotted spined bug Haryomorpha mista Uhler Brown-marmorated Stink bug Lagynotomus elongatus Dallas Rice stink bug Nezara viridula Linnv Southern green Stink bug Cletus trigonus Thunberx Slender rice bug Stephanitis nashi Esaki et Takeya Japanese pear lace bug Stephanitis pyrioides Scott
Azalea lace bug Psylla pyrlsuga FArster Pear sucker Psylla mali Schmidberxer Apple Sucker Aleurolobus taonabae Kuwana Grape whitefly Dialeurodes citri Ashmead Citrus whitefly Trialeurodes vaporariorum Westwood Greenhouse Whitefly Aphis gossypii Glover Cotton aphid Brevicoryne brassicae Linnv Cabbage aphid Myzus Persicae Sulzer Green peach aphid Rhopalosiphum maidis Fitch Corn leaf aphid Icerya purchasi Maskell Cottonycushion scale Planococcus citri Risso citrus mealybug Unaspis yanonensis Kuwana arrowhead scale 2 Lepidoptera Canephora asiatica Staudinger Mulberry bagworm Spulerina astaurcta Meyrick Pear bark miner Phyllonorycter ringoneella Matsumura Apple leafminer Plut ella xylostella Linnv Diamond back moth Promalactis inopisema Butler Cotton seedworm Adoxophyes orana Fischer von
SMALLER TEA TEA TEA TORTRIX BACTRA FURFURANA HAWORTH Pod Borer CNAPHALOCROCROCIS Medinalis Guenve (Cobremeiga) Rice Leaf Roller Etiela Zinckenella Treitschke furnacalis Guenve Oriental corn borer Pleuroptya derogata Fabricius Cotton leaf roller Hyphantria cunea Drury Fall webworm Abraxas miranda Butler Magpie moth Lymantria dispar japonica Motschulsky Gypsy moth Phalera fiavescens Bremer et Gray Cherry caterpillar Agrotis segetum Denis et Schiffer mBller Cutworm Helicoverpa armigera HBbner Cotton boll worm Pseudaletia separata Walker Armyworm Mamestra brassicae Linnv Cabbage armyworm Plusia nigrisigna Walker Beet semi −looper Spodoptera litura Fablicius Common cutworm Parnara guttata Bremer et Grey Rice skipper Pieris rapae crucivora Boisduval Common cabbageworm Chilo suppressalis Walker Rice stem borer 3 Coleoptera Melanotus fortnumi Candvze Sweetpotato wireworm Anthrenus verbasci Linnv Varied carpet beetle Tenebroides mauritanicus Linnv Cadelle Lyctus brunneus Stephens Powder post beetle Henosepilachna vigintioctopunctata
Fablicius 28−spotted lady beetle Monochamus alternatus Hope Japanese pine sawyer Xylotrechus pyrrhoderus Bates Grape borer Aulacophora femoralis Motschulsky Cucurbit leaf beetle Oulema oryzae Kuwayama Rice leaf beetle Phyllotreta striolata Fablicius Striped flea beetle Callosobruchus chinensis Linnv Azuki bean weevil Echinocnemis squameus Billberg Rice plant weevil Sitophilus oryzae Linnv Rice weevil Apoderus erythrogaster Vollenhoven M) Small black leaf−cut
weevil Rhynchites heroes Roelofs Peach curculio Anomala cuprea Hope Cupreous chafer Popillia japonica Newman Japanese beetle 4 Hymenoptera Athalia rosae japonensis Rohwer Cabbage sawfly Arge similis Vollenhoven Yuu Range) Azalea argid sawfly Arge pagana Panzer Rose argid sawfly 5 Diptera Tipula aino Alexander Rice crane fly Culex pipiens fatigans Wiedmann House mosquito Aedes aegypti Linnv Yellow −fever mosquito Apshondylia sp. Soybean pod gall midge Hylemya antiqua Meigen Onion maggot Hylemya platura Meigen Seed corn maggot Musca domestica vicina Macquart House fly Dacus cucurbitae Coquillett Melon fly Chlorops oryzae Matsumura Rice stem maggot Agromyza oryzae Munakata Rice leafminer 6 Siphonaptera Pulex irritans Linnv Human
flea Xenopsylla cheopis Rothschild Tropical rat flea Ctenocephalides canis Curtis Dog flea 7 Thysanoptera Scirsothrips dorsalis Hood Yellow tea thrips Thrips tabaci Lindeman Onion thrips Chloethrips oryzae Williams Rice thrips 8 Anoplura Pediculus humanus corporis De Geer Body louse Phthirus pubis Linnv Crab louse Haematopinus eurysternus Nitzsh Short-nosed cattle louce 9 Psocoptera Trogium pulsatsrium Linnv Larger pale booklouse Liposcelis bostrychophilus Badonnel Flattened booklice 10 Orthoptera Gryllotalpa africana palisot de Beauvois
African mole cricket Locusta migratoria danica Linnv Asiatic locust Oxya yezoensis Shiraki Short-winged rice grass hopper 11 Dictyoptera Blattella germanica Linnv German cockroach Periplaneta fuliginosa Serville Smoky -brown cockroack 12 Acarina (Dani eyes) BOOPHILUS MICROPLUS CANESTRINI (Oshimadani) Bull Tick PolyPhagotarsonemus Latus Banks Hus Citri McGregor (Mandarin spin) Citrus red mite tetranychus cinnabarinus BoissDuVAL (Nissenami haudit) Carmine Spider Mite Tetranychus Urticae Koch ( Two-spotted spider mite Rhizoglyphus echinophus Fumouze et
Robin Bulb mite When actually applying the compound of the present invention, it can be used alone without adding other ingredients, but in order to make it easier to use as a pesticidal agent, it may be formulated with a carrier. It is common to dilute and apply as necessary. The compounds of the present invention can be formulated into emulsions, wettable powders, powders, granules, and fine granules by methods well known in the art in accordance with general agricultural chemicals without any special conditions. , oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.),
It can be prepared in any form such as a fogging agent, non-heated fumigation agent, poison bait, etc., and can be used for various purposes depending on the purpose. Furthermore, by combining two or more of these compounds of the present invention, it is possible to express superior insecticidal and acaricidal activity, and it is also possible to express superior insecticidal and acaricidal activity, and to use other physiologically active substances,
For example, allethrin, N-(chrysansemoylmethyl)-3,4,5,6-tetrahydrophthalimide, 5-benzyl-3-furylmethyl chrysanthemate, 3-phenoxybenzyl chrysanthemate, 5-propargylfur Furyl chrysanthemate, other known cyclopropane carboxylic acid esters, 3-phenoxybenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylate, 3-phenoxy-α
-cyanobenzyl 2,2-dimethyl-3-(2,
2-dichlorovinyl)-cyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-1-carboxylate, 3-phenoxy -α-cyanobenzyl α-
Synthetic pyrethroids such as isopropyl-4-chlorophenylacetate and their various isomers or pyrethrum extract, 0,0-diethyl-0-
(3-oxy-2-phenyl-2H-pyridazine-
6-yl) phosphorothioate (Mitsui Toatsu Chemical registered trademark Offnack), 0,0-dimethyl-0-
(2,2-dichlorovinyl)-phosphate (DDVP), 0,0-dimethyl-0-(3-methyl-4-nitrophenyl) phosphorothioate, diazinon, 0,0-dimethyl-0-4-cyanophenyl phosphorothioate, 0,0-dimethyl-S-[α-(ethoxycarbonyl)benzyl]phosphorodithioate, 2-methoxy-4H-1,
Organophosphorus insecticides such as 3,2-benzodioxaphosphorine-2-sulfide, 0-ethyl-0-4-cyanophenyl phenylphosphonothioate, 1-naphthyl-N-methylcarbamate (NAC), m-Tolyl-N-methylcarbamate (MTMC), 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-dimethylcarbamate (pyrimer), 3,4-dimethylphenyl N-
Carbamate insecticides such as methyl carbamate and 2-isopropoxyphenyl N-methyl carbamate, other insecticides, acaricides or fungicides, nematicides, herbicides, plant growth regulators, fertilizers,
By mixing it with BT agents, insect hormone agents, other agricultural chemicals, etc., it is possible to create a multipurpose composition with even greater efficacy, and a synergistic effect can also be expected. Furthermore, for example α-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2
-propyltoluene {piperonyl butoxide},
1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene {sulfoxide}, 4-(3,4-methylenedioxyphenyl)-5-methyl-1,3-dioxane { safroxane}, N-(2-ethylhexyl)-bicyclo(2,2,1)hept-5-ene-2,3-carboximide {MGK-264}, octachlorodipropyl ether {S-421}, isovol Its potency can also be increased several times by adding known synergists for pyrethroids, such as neilthiocyanoacetate {Garnite}. The compounds of the present invention have high stability against light, heat, oxidation, etc., but if necessary, antioxidants or ultraviolet absorbers, such as phenol derivatives such as BHT and BHA, bis-phenol derivatives, and phenyl-α- A composition with more stable effects can be obtained by adding an appropriate amount of arylamines such as naphthylamine, phenyl-β-naphthylamine, a condensate of phenetidine and acetone, or benzophenone compounds as a stabilizer. The insecticide and acaricide of the compound of the present invention is
0.0001-99% by weight, preferably 0.001-50% by weight
Contain. Next, some examples of formulations in which the compound of the present invention is used as an insecticide or acaricide are shown, but the present invention is not limited to these. All "parts" indicate parts by weight. Formulation example 1 Compounds of the present invention Table 1, compound numbers 1 to 17,
20 parts of compounds 19 to 105 and 107 to 109 (the same applies hereinafter), 20 parts of Solpol SM-100 (a surfactant manufactured by Toho Chemical Co., Ltd.), and 60 parts of xylol are stirred and mixed to prepare an emulsion. Formulation Example 2 1 part of the compound of the present invention is dissolved in 10 parts of acetone, 99 parts of clay for powders are added, and the acetone is evaporated to form a powder. Formulation Example 3 Add 5 parts of a surfactant to 20 parts of the compound of the present invention, mix well, then add 75 parts of diatomaceous earth, and stir and mix in a Raikai machine to prepare a wettable powder. Formulation Example 4 Add 2 parts of meta-tolyl N-methyl carbamate to 0.2 parts of the compound of the present invention, and further add 0.2 parts of PAP (registered name of Nihon Kagaku Kogyo, physical property improver) to 0.2 parts of the compound of the present invention, dissolve in 10 parts of acetone, and prepare powder clay. Add 97.6 parts of and stir and mix in a Raikai machine, and evaporate the acetone to form a powder. Formulation Example 5 0.2 parts of the compound of the present invention was added with 2 parts of Ofnatsu (registered trade name of Mitsui Toatsu Chemical), and then PAP (mentioned above) was added.
Add 0.2 parts, dissolve in 10 parts of acetone, add 97.6 parts of powder clay, stir and mix in a Raikai machine, and evaporate the acetone to form a powder. Formulation Example 6 Piperonyl butoxide is added to 0.1 part of the compound of the present invention.
Add 0.5 part and dissolve in white kerosene to make the total 100 parts to make an oil solution. Formulation Example 7 Add 5 parts of Solpol SM-200 (mentioned above) to 0.5 parts of the compound of the present invention and 5 parts of Ofnuck (mentioned above), and dissolve in 89.5 parts of xylene to obtain an emulsion. Formulation example 8 0.4 part of the compound of the present invention, piperonyl butoxide
Mix and dissolve 2.0 parts of kerosene, 6 parts of xylol, and 7.6 parts of deodorized kerosene, fill it into an aerosol container, attach the valve part, and pressurize and fill 84 parts of propellant (liquefied petroleum gas) through the valve part to create an aerosol. Formulation Example 9 When 0.05 g of the compound of the present invention is dissolved in an appropriate amount of chloroform and evenly adsorbed onto the surface of asbestos measuring 2.5 x 1.5 cm and 0.3 mm thick, a fiber fumigation insecticidal composition heated on a hot plate is obtained. Formulation Example 10 0.5 g of the compound of the present invention was dissolved in 20 ml of methanol, and an incense stick carrier (Tab flour: Leek flour: Wood flour: 3:5:
Stir and mix 99.5 parts of (mixed at a ratio of 1 part) uniformly,
After evaporating the methanol, add 150 ml of water, mix well, mold and dry to make a mosquito coil. Formulation Example 11 1 part of the compound of the present invention, 3 parts of Offnack (mentioned above),
Mix 92 parts of clay with 2 parts of Celogen 7A (Daiichi Kogyo Seiyaku brand name), 2 parts of Sunextract (Sanyo Kokusaku Pulp Product), add water, granulate it, and size it to the optimal particle size to make granules. . When applying the compound of the present invention, the amount of the active ingredient is generally 300g to 1g per 10 ares, preferably 100g to 2g, more preferably 20g to 5g.
It is g. Next, in order to clarify that the compound of the present invention has excellent insecticidal and acaricidal effects, has low toxicity to mixed-breed animals, and has relatively low toxicity to fish, test examples are presented below. show. Sample: 20 parts of the compound of the present invention and Solpol SM-
200 (surfactant manufactured by Toho Chemical Co., Ltd.) 20 parts xylol
60 parts were added and these were thoroughly stirred and mixed. Dilute the emulsion with distilled water to each test concentration. For the fish toxicity test, the raw material of the test compound is dissolved in acetone to make a 1% solution, and a predetermined amount is added to water. For toxicity tests on mice, the drug substance is dissolved or suspended in corn oil. Note that the comparative compounds (a) to (i) shown below were used as control compounds and were subjected to the test in the same manner as the compounds of the present invention. (Publicly known Japan Pesticide Information No.33,
13 (1977)) (Known U.S. Pat. No. 4,073,812) (C) Pyrethrin (d) Ofnac (supra) (e) MTMC (supra) (f) Methomyl (S-methyl M-(methylcarbamoyloxy)thioacetamidate) (g) DDVP (Ibid.) (h) Ortolan (0, S-dimethyl N-acetyl phosphoroamide thiolate) (i) Permethrin [3-phenoxybenzyl 2,
2-dimethyl-3-(2,2-dichlorovinyl)
-Cyclopropane-1-carboxylate] Test Example 1 Effect on Spodoptera trifoliata Emulsions of each test compound prepared according to Formulation Example 1 were prepared at concentrations of 100 and 20 ppm. Saipotato leaves were immersed in each chemical solution for 10 seconds, placed in air-dried plastic cups with a diameter of 10 cm, and 2nd instar larvae of Spodoptera japonica were released and left in a constant temperature 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 as the average value of three consecutive results. The test compounds are indicated by compound numbers in Table 1 above.

【table】

【table】

[Table] Test Example 2 Effect of immersion in Spodoptera larvae Same as Test Example 1, 100 and 100% of each test compound
A drug solution with a concentration of 20 ppm was prepared. Spodoptera 2nd and 5th instar larvae were immersed in the above chemical solution for 5 seconds, and after removing excess chemical solution with filter paper, they were released into plastic cups prepared in advance, fed with artificial food, and left in a constant temperature room at 25℃. did. 24 hours after the treatment, the number of live and dead insects was investigated, and the mortality rate was calculated. The results are shown as the average value of three series.

[Table] Test Example 3 Effect on resistant leafhopper and susceptible leafhopper Young paddy rice seedlings (2 to 3 true leaves) were grown hydroponically in pots with a diameter of 5 cm, and 100% and Each pot was treated with 3 ml/pot of a 20 ppm drug solution using a sprayer. After air-drying, the seedlings were covered with a wire mesh cylinder, and the resistant leafhopper (native to Nakagawa) and susceptible leafhopper (native to Megasaki) were isolated.
Ten female adults were released per pot and left in a glass greenhouse. 24 hours after treatment, the number of live and dead insects was investigated, and the mortality rate was calculated. Linkage was shown as the average value of three runs.

【table】

【table】

[Table] Test Example 4 Effect on diamondback moth A plastic cup was covered with Cilantro leaves and 10 third instar diamondback moth larvae were released. A chemical solution with a concentration of 100 and 20 ppm of each test drug prepared in the same manner as in Test Example 1 was added to the spray tower per cup.
ml was sprayed. After spraying, the cup was covered, and 24 hours later, the number of live and dead insects was counted, and the mortality rate was calculated. Linkage was shown as the average value of triplicates.

[Table] Test Example 5 Effect on Green Peach Aphid Potted eggplant seedlings (3 to 4 true leaves) were inoculated with Green peach aphid and allowed to grow. The number of insects was measured, and each test drug prepared in the same manner as Test Example 1 was tested.
100ppm concentration chemical solution per pot with a spray gun
ml processed. After treatment, the plants were left in a glass greenhouse, and the number of live and dead insects was investigated after 24 hours to determine the mortality rate. The results are A, 95 if the average mortality rate of three series is 95% or more.
~80% was designated as B, 80 to 50% was designated as C, and 50% or less was designated as D.

【table】

[Table] Test Example 6 Effect on adult two-spotted spider mites Ten adult two-spotted spider mites were placed on water-soaked absorbent cotton (2 cm x 2 cm) with leaf discs of green bean leaves punched out with a cork borer (diameter 15 mm). 3 ml of each test drug at a concentration of 100 ppm was applied to each sample using a spray tower. After treatment, the specimens were left in a constant temperature room at 25°C, and the number of living and dead insects was investigated 24 hours after treatment to determine the adult killing rate. The results are shown as the average value of three series.

【table】

[Table] Test Example 7 Effect on German cockroaches Each test compound was applied at 50 mg/m ² and 10 mg/m ² to the bottom of a waist-high shear plate measuring 9 cm in diameter and 9 cm in height.
After air-drying, 10 male German cockroaches were released and left in a constant temperature room at 25°C, and after 24 hours, the number of dead insects was counted. The inner walls of the shear were treated with butter to prevent insects from escaping. The results are shown as the average value of two series.

【table】

[Table] Test Example 8 Fish Toxicity Fill a water tank with width 60cm, length 30cm, and height 40cm.
After releasing 10 mature carp fish with a body length of approximately 5 cm and allowing them to acclimate, each test chemical was added to the water at a concentration of 10, 1, and 0.1 ppm, and after 48 hours, the number of live and dead fish was investigated.
We looked at the effects on fish.

【table】

[Table] Example 9 of drug concentration test resulting in death Toxicity test A prescribed amount of the drug substance (0.2 ml/10 g body weight) dissolved or suspended in corn oil was orally administered to male mice (body weight 19-23 g), and the number of deaths was determined after 7 days. We investigated the effect on mice.

[Table] *Dose that kills half of the number of test animals

Claims (1)

[Claims] 1. General formula [] [Wherein, Ar is an unsubstituted or lower alkyl-substituted naphthyl group, or an unsubstituted or halogen atom,
Lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkenyl group, lower haloalkenyl group, lower alkenyloxy group, lower haloalkenyloxy group, lower alkynyl group, Represents a phenyl group substituted with a lower alkynyloxy group, a lower alkoxy lower alkyl group, a lower acyl group, a lower alkoxycarbonyl group, a cyano group, a nitro group or a methylenedioxy group, R represents a methyl group or an ethyl group, and Y represents an oxygen atom or a sulfur atom, and B is a general formula [] or a general formula [] (In the formula [], Z represents an oxygen atom, a sulfur atom, a carbonyl group, or a methylene group, and R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. n represents an integer from 1 to 5. .Herein, when n is 2 or more, R ¹ may be the same or different. However, cases where the general formula [] is 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether or the general formula [] are not included. (In the formula [], R represents the above meaning, R ²
represents a halogen atom or a lower alkyl group,
m represents 1 or 2. 2-arylpropyl ether derivatives and thioether derivatives represented by (including cases where R ² is the same or different when m is 2)]. 2. The compound according to claim 1, wherein in the general formula [], R is a methyl group. 3 In the general formula [], Ar is the general formula [] [In the formula, R ³ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a methylenedioxy group, a lower alkylthio group, a nitrile group, or a nitro group, and p is 1 Represents an integer between 3 and 3.
When p is 2 or more, R ³ may be the same or different. ] The compound according to claim 1, characterized in that it is represented by: 4 In general formula [], R ³ of general formula []
The compound according to claim 1, 2 or 3, wherein is a halogen atom, a lower alkoxy group or a lower haloalkoxy group. 5. The compound according to claim 1, wherein in the general formula [], Y is an oxygen atom. 6. The compound according to claim 1, wherein in the general formula [], Z in the general formula [] is an oxygen atom. 7 In general formula [], R ¹ of general formula []
2. The compound according to claim 1, wherein is a hydrogen atom or a halogen atom. 8 A compound represented by the general formula [] [Formula] B-CH ₂ -D [] [Wherein, Ar is an unsubstituted or lower alkyl-substituted naphthyl group, or an unsubstituted or halogen atom,
Lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkenyl group, lower haloalkenyl group, lower alkenyloxy group, lower haloalkenyloxy group, lower alkynyl group, Represents a phenyl group substituted with a lower alkynyloxy group, a lower alkoxy lower alkyl group, a lower acyl group, a lower alkoxycarbonyl group, a cyano group, a nitro group or a methylenedioxy group, R represents a methyl group or an ethyl group, and B is general formula [] or general formula [] (In the formula [], Z represents an oxygen atom, a sulfur atom, a carbonyl group, or a methylene group, and R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. n represents an integer from 1 to 5. .Herein, when n is 2 or more, R ¹ may be the same or different. One group of groups A and D represents a halogen atom, and the other group Y-M group (in the formula, Y represents an oxygen atom or a sulfur atom, and M represents a hydrogen atom or an alkali or alkaline earth metal atom). or both represent a hydroxyl group] [In the formula, Ar, R, Y and B represent the above meanings. However, cases where the general formula [] is 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether or the general formula [] are not included. (In the formula [], R represents the above meaning, R ²
represents a halogen atom or a lower alkyl group,
m represents 1 or 2. When m is 2, R ² may be the same or different.)] 9 In the general formula [], the group A is a Y-M group [wherein Y and M represent the above meanings],
9. The production method according to claim 8, wherein in the general formula [], the group D is a halogen atom. 10 In the general formula [], group A is a halogen atom, and in the general formula [], group D is Y-H
In the case where [Y represents the above meaning],
9. The production method according to claim 8, characterized in that the compound represented by the general formula [] and the compound represented by the general formula [] are reacted in the presence of dimethyl sulfoxide or sulfolane. 11. The manufacturing method according to claim 8, wherein in the general formula [] and the general formula [], both the group A and the group D are hydroxyl groups. 12 General formula [] [Wherein, Ar is an unsubstituted or lower alkyl-substituted naphthyl group, or an unsubstituted or halogen atom,
Lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkenyl group, lower haloalkenyl group, lower alkenyloxy group, lower haloalkenyloxy group, lower alkynyl group, Represents a phenyl group substituted with a lower alkynyloxy group, a lower alkoxy lower alkyl group, a lower acyl group, a lower alkoxycarbonyl group, a cyano group, a nitro group or a methylenedioxy group, R represents a methyl group or an ethyl group, and Y represents an oxygen atom or a sulfur atom, and B is a general formula [] or a general formula [] (In the formula [], Z represents an oxygen atom, a sulfur atom, a carbonyl group, or a methylene group, and R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. n represents an integer from 1 to 5. .Herein, when n is 2 or more, R ¹ may be the same or different. However, cases where the general formula [] is 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2methylpropyl ether or the general formula [] are not included. (In the formula [], R represents the above meaning, R ²
represents a halogen atom or a lower alkyl group,
m represents 1 or 2. An insecticide or acaricide characterized by containing a ² -arylpropyl ether derivative and/or a thioether derivative as an active ingredient.