JPH032851B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel 2-arylpropyl ether derivatives. More specifically, one aspect of the present invention is the general formula [] (In the formula, Ar represents a phenyl group, a phenyl group substituted with a phenyl group, a phenoxy group, a lower cycloalkyloxy group, a lower alkoxy lower alkoxy group, a lower alkoxy lower alkylthio group, a lower haloalkoxycarbonyl group, or a tetrahydrofuryloxy group.) It relates to a 2-arylpropyl ether derivative represented by Pesticides have played an extremely important role in improving agricultural productivity, and the appearance of synthetic organic pesticides has completely changed the food situation for humankind, bringing great benefits in terms of preventing infectious diseases transmitted by insects. However, organochlorine insecticides DDT and BHC
Their use is limited because they remain in the environment for a long time after use, and organophosphorus insecticides and carbamate insecticides, which have recently appeared, are widely used, but there are various Problems of resistance to these insecticides have arisen in several insect pests. In addition, difficult-to-control pests are appearing in some areas, and it is expected that problems such as drug-resistant pests will continue to spread and become more serious in the future. To this day, as humans seek to maintain a sufficient supply of food necessary for the foundation of their civilization and for their further development, the emergence of drugs with superior insecticidal activity has been urgently needed. There is. In recent years, synthetic pyrethroid insecticides have been in the spotlight against this background. It has excellent insecticidal power and is highly effective against pests resistant to organic phosphorus agents or carbamate agents, and is characterized by relatively low toxicity to humans and livestock. However, the fatal drawback of this synthetic pyrethroid insecticide is that it is extremely toxic to fish, which limits its range of use. Furthermore, they are more expensive than conventionally developed insecticides. Agrochemicals that are desired in the future must be ones that solve the above-mentioned drawbacks. It is highly safe, leaves no residue, decomposes quickly and does not pollute the environment, has high activity against the current problem of drug-resistant pests that are difficult to control, and can be manufactured at a low cost. It is desired. The present inventors have devoted themselves to research and development of insecticidal and acaricidal agents that meet the above conditions, and have found that 2-phenylpropyl ether derivatives and thioether derivatives have high insecticidal and acaricidal activity, are fast-acting, and have no residue. In addition to having excellent characteristics in terms of effectiveness,
It has been found that the compound has low toxicity not only to humans and livestock, but also to fish, and can be put to practical use at a relatively low cost. After further research on this group of compounds and their insecticidal properties, we found that the combination of two types of alcohol residues was selective for Coleoptera, Lepidoptera, Hemiptera, Termites, Diptera, Acari, etc. It has been found that the present invention provides an excellent pest control composition that exhibits non-selective efficacy, has a broad insecticidal spectrum, and has extremely low toxicity to humans and livestock. In addition, many of them were found to have low toxicity to fish, leading to the completion of the present invention. The compound of the present invention has an active structure different from that of conventional agricultural chemicals, and is effective against sanitary pests such as flies, mosquitoes, and cockroaches, as well as planthoppers, leafhoppers, armyworms, diamondback moths, leafhoppers, aphids, and caterpillars. It is highly effective against agricultural pests such as spider mites, especially the black leafhopper, and is also extremely effective against grain storage pests such as the white mite, white-spotted moth, and brown elephant, animal-parasitic lice, and mites, and is also effective against other pests. Furthermore, the compound of the present invention has excellent rapid action and residual action, and also has a flushing effect. The compound of the present invention not only knocks down and kills pests, but also has repellent properties and removes pests from the host.
It also has a repellent effect, and has the great advantage of not causing any phytotoxicity to Solanaceae plants, such as fuenvalerate, which is one of the representative synthetic pyrethroids. In addition, it has low toxicity to mammals. Some of the compounds of the present invention are also highly safe for fish, and are not only suitable for pest control in rice fields, but also
Extermination of aquatic pests such as mosquitoes and blackfly larvae, or lakes,
Even when using aircraft to exterminate pests in large areas dotted with swamps, ponds, and rivers, it can be used without the risk of killing fish living there. Therefore, the insecticides and acaricides containing the compounds of the present invention can be applied to a wide range of fields, including agricultural and horticultural pests, storage pests, sanitary pests, house pests, forest pests,
Some of them are highly active as insecticides and acaricides against aquatic pests, are extremely safe, and can be put to practical use in various formulations at low cost. The 2-arylpropyl ether derivative represented by the general formula [] according to the present invention is a new compound. The phenyl group represented by Ar represents a phenyl group which may be optionally substituted with the same or different substituents shown below. Substituents include phenyl, phenoxy, cycloalkyloxy,
Examples include alkoxyalkoxy, alkoxyalkylthio, haloalkoxycarbonyl, and tetrahydrofuryloxy groups. Specific examples of the aryl group are shown below, but are not limited to the examples. That is, 4-cyclopentyloxyphenyl group, 4-biphenyl group, 4
-Phenoxyphenyl group, 4-cyclohexyloxyphenyl group, 4-methoxymethoxyphenyl group, 4-ethoxymethoxyphenyl group, 4-(1
-ethoxyethoxy)phenyl group, 4-(1-methoxyethoxy)phenyl group, 4-(2-ethoxyethoxy)phenyl group, 4-(2,2,2-trifluoroethoxycarbonyl)phenyl group, 4
Examples include -methoxymethylthiophenyl group, 4-(tetrahydro-3-furyloxy)phenyl group, and 4-ethoxymethylthiophenyl group. Next, the method for producing the compound of the present invention will be described in detail as follows. A compound represented by the general formula () is expressed by the general formula () [In the formula, Ar represents the above meaning, one of the groups A and B represents a halogen atom,
The other group represents an O-M group (in the formula, M represents a hydrogen atom or an alkali or alkaline earth metal atom), or both represent a hydroxy group], thereby forming a compound of the general formula [ The 2-arylpropyl ether derivative represented by the following formula is easily produced. That is, the general formula [] [where the group A is O-H
Alcohol and general formula [] when representing a group]
When reacting the halide [in the formula, when group B represents a halogen atom], the desired 2-arylpropyl ether is obtained by reacting it in the presence of a base as a deoxidizing agent in an appropriate solvent at room temperature or under heating. derivatives can be obtained. The bases mentioned here refer to alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal hydrides, alkali metal alcoholates, alkali metal oxides, alkali metal carbonates, sodium amide, triethylamide, etc. Silver oxide can also be used as an agent. Examples of solvents include water, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, and petroleum benzene, halogenated hydrocarbons such as chloroform and dichloromethane, and dimethylformamide and dimethylsulfoxide. Aprotic polar solvents, lower alcohols such as methanol and ethanol, ethers such as diisopropyl ether, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and dioxane, nitriles such as acetonitrile and propionitrile, acetone, diisopropyl ketone Ketones such as the following can be used. Furthermore, the desired 2-arylpropyl ether derivative can also be obtained in good yield by using a phase transfer catalyst such as tetra-n-butylammonium bromide or triethylbenzylammonium bromide as a catalyst. General formula [] [In the formula, group A is an OM group (in the formula,
When M is not a hydrogen atom), the alcoholate of the general formula [] [where the group B represents a halogen atom] is reacted with the reaction in the above solvent at room temperature or under heating. 2-arylpropyl ether derivatives can be obtained. If the reactivity is poor, it is also suitable to add a catalytic amount of potassium iodide, copper iodide, etc. Halide of general formula [] [where group A represents a halogen atom] and general formula [] [where group B represents an OM group (in the formula, M represents the above meaning)]
In the case of reacting with an alcohol or an alcoholate, the reaction can be carried out in the same manner as described above. In particular, when reacting a halide of the general formula [] [in which the group A represents a halogen atom] with an alcohol of the general formula [] [in the formula, the group B represents an O-H group], an aprotic The desired 2-arylpropyl ether derivative can be obtained in good yield by the reaction in the presence of a polar solvent, preferably dimethyl sulfoxide or sulfolane, in the presence of a base as a deoxidizing agent, and under heat. Alcohol of general formula [] [in the formula, when group A is a hydroxyl group] and general formula [] [in the formula,
When the group B is a hydroxyl group], a dehydration reaction can be carried out in the presence of a catalyst to obtain a 2-arylpropyl ether derivative. As the catalyst, acid catalysts such as sulfuric acid, hydrochloric acid, aromatic sulfonic acid, sulfonic acid chloride, boron trifluoride, and aluminum chloride can be used. Iodine, solid acid catalyst (alumina)
Titanium oxide, etc.), dimethyl sulfoxide, alumina, sulfamide, ion exchange resins, etc. can also be used as dehydration catalysts. If necessary, it is preferable to carry out the reaction in an inert solvent such as benzene or toluene that is azeotropic with water while removing produced water under reflux. In addition, an alcohol of the general formula [] [where the group A represents a hydroxyl group] is added to the alcohol of the general formula [] [where the group A represents a hydroxyl group] in the presence of a dehydrating agent and, if necessary, a catalyst. A 2-arylpropyl ether derivative can also be obtained by reacting with an alcohol (in the case shown below). As the dehydrating agent, for example, N,N-substituted carbodiimide, especially N,N-dicyclohexylcarbodiimide is preferable, and as the catalyst, for example, cuprous chloride is preferable. The reaction is carried out in the presence of a suitable inert solvent or diluent at room temperature or under heat. Suitable solvents or diluents include, for example, ethers such as 1,2-diethoxyethane, dioxane, and tetrahydrofuran; aprotic polar solvents such as dimethylformamide, hexamethylphosphonic acid triamide, and dimethyl sulfoxide; acetone;
Examples include ketones such as methyl ethyl ketone and cyclohexanone. In addition, as a method for producing 2-arylpropyl ether derivatives, metal alcoholates or sulfonic acid esters of alcohols of the general formula [] [in which group A represents a hydroxyl group] and A method for reacting an alcohol with the general formula [when B is a hydroxyl group] [where the group A is a hydroxyl group]
There is a method of reacting the alcohol with the metal alcoholate or sulfonic acid ester of the alcohol of the general formula [ ] (where group B is a hydroxyl group), but this method is disadvantageous in terms of yield. The starting materials of the general formula [] are known or prepared analogously to known methods described in the literature. That is, the alcohol represented by the general formula [] [in which the group A represents a hydroxyl group] is, for example, the corresponding arylacetonitrile Ar.CH ₂ alkylated with,
The resulting nitrile is then hydrolyzed to convert it into the corresponding carboxylic acid, and the carboxylic acid is reduced. It is also obtained by converting a halide obtained by adding methallyl halide to an aryl (in the case where group A represents a halogen atom in the general formula []) into an alcohol. An example manufacturing route is shown diagrammatically below. 50% NaOH or KOH phase transfer catalyst Reference Roczniki Chem., 39(9), 1223
(1965) (Pol) [Chemical Abstract 64, 12595, h
(1966)] Manufactured according to route (1) below. [In formula [], group A is a halogen atom] References Chem.Ber., 94, 2909 (1961) [] (1) Mg [] [Group A=OH] (2)O ₂ (3)H ⁺ aO References J.Am.Chem.Soc.65, 1469 (1943) Reference Chem.Ber., 94, 2609 (1961) [][Group A=OH] is synthesized by the following route (3). 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). General formula [] [In the formula, group A represents an O-M group,
When M is not a hydrogen atom], the metal alcoholate can be prepared by a conventional method, for example, with a metal hydride such as sodium hydride and the general formula [] [where the group A is O-].
M group, where M is a hydrogen atom] can be easily obtained by reacting an alcohol. Alcohols of the general formula [] [where group B is a hydroxyl group] are known as alcohol components of synthetic pyrethroids. Next, the method for producing the 2-arylpropyl ether derivative of the present invention will be described in more detail with reference to Examples. Example 1 (Etherification method A) 3-phenoxybenzyl 2-[4-(cyclohexyloxy) Synthesis of phenyl]-2-methylpropyl ether 0.50 g of sodium hydride (60% in oil) was added to 20 ml of dry acetonitrile, and then 2-[4
-(Cyclohexyloxy)phenyl]-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 2.7 g of 3-phenoxybenzyl bromide in 10 ml of acetonitrile was added.
The mixture was added dropwise over 10 minutes, and the mixture was further heated under reflux for 1 hour.
After cooling to room temperature, it was poured into water and extracted with toluene. After washing the toluene extract with saturated saline,
Dry. 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-hexane [1:1]) to obtain the desired ether (yield 72%). Ta. D ^20.1 _D 1.5516 Elemental analysis value: C ₂₉ H ₃₄ O ₃ C H Calculated value (%) 80.89 7.96 Measured value (%) 81.13 7.78 Example 2 (Etherification method B) 3-Phenoxybenzyl 2-(4- Synthesis of (phenoxyphenyl)-2-methylpropyl ether Sodium hydride (60% in
Add 0.50g of 2-(4-
A solution of 2.42 g (phenoxyphenyl)-2-methylpropyl alcohol/10 ml of 25% DMF-toluene was added dropwise over 15 minutes. After continuing stirring for 10 minutes, 3.9 g of 3-phenoxybenzyl bromide/
10ml toluene solution was added dropwise over 20 minutes. moreover,
After 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. The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography on 120 g of silica gel (developing solvent: toluene-hexane [1:1]) to obtain the desired ether (yield 79%). Ta. n ^19.7 _D 1.5930 Elemental analysis value: C ₂₉ H ₂₈ O ₃ C H Calculated value (%) 82.05 6.65 Measured value (%) 82.22 6.47 Example 3 (Etherification method C) 3-Phenoxybenzyl 2-[4- ethoxymethoxy)phenyl]-2-methylpropyl
Synthesis of ether Add 30 g of 50% sodium hydroxide, 4.5 g of 2-[4-(ethoxymethoxy)phenyl]-2-methylpropyl alcohol, 4.4 g of 3-phenoxybenzyl chloride and 1.0 g of tetrabutylammonium bromide, The mixture was heated under reflux at ℃ for 1 hour.
After cooling to room temperature, water was added, extracted with toluene, and washed with water. After drying the toluene extract, the toluene was distilled off under reduced pressure and the resulting crude ether was purified using silica gel 160.
The target ether was purified by column chromatography (developing solvent: toluene-hexane [1:1]) (yield: 81%). n ^20.0 _D 1.5330 Elemental analysis value: C ₂₆ H ₃₀ O ₄ C H Calculated value (%) 76.82 7.44 Measured value (%) 76.58 7.63 Example 4 (Etherification method D) 3-Phenoxybenzyl 2-[4- Synthesis of (cyclopentyloxy)phenyl]-2-methylpropyl ether 2-[4-(cyclopentyloxy)phenyl]
A mixture of 4.7 g of -2-methylpropyl alcohol, 4.4 g of 3-phenoxybenzyl chloride, 1.0 g of triethylbenzylammonium bromide, and 20 g of 50% sodium hydroxide was stirred at 50°C for 2 hours. After adding water and benzene and shaking well, the mixture was separated. The benzene layer was washed with water and dried. The crude ether obtained by distilling off benzene under reduced pressure was purified by silica gel.
160g column chromatography (developing solvent:
The desired ether (yield: 85%) was obtained by purification using toluene-hexane (1:1). n ^20.1 _D 1.5753 ν ^neat _nax (cm ^-1 ) 1615, 1520, 1500, 1260, 1225
，
1110. δ ^CCl _4TMS (ppm): 1.28 (6H, s), 1.5~2.0 (8H,
m),
3.31 (2H, s), 4.36 (2H, s), 4.62 (1H,
m), 6.6-7.3 (13H, m). Elemental analysis value: _C28H32O3CH Calculated value (%) _80.73 7.74 Measured value ₍ %) 80.55 7.89 Example 5 (Etherification method E) 3-Phenoxybenzyl 2-(4-phenylphenyl group)- Synthesis of 2-methylpropyl ether 9.98 g of 4-phenylneophyl chloride, 3-
9.67 g of phenoxybenzyl alcohol, 3.9 g of 45% sodium hydroxide and dimethyl sulfoxide
48g was heated and stirred at 140°C for 3 hours. 1.8 g of 45% sodium hydroxide was added, and the reaction was continued at the same temperature for an additional 4 hours. The reaction solution was poured into water, extracted with benzene, and the benzene extract was washed with water and then dried. The crude ether obtained by distilling off benzene under reduced pressure was subjected to column chromatography on 400 g of silica gel (developing solvent: toluene-hexane [1:1]).
The desired ether (yield: 82% vs. consumed 4-phenylneofyl chloride) was obtained. n ^19.6 _D 1.6066 Elemental analysis value: C ₂₉ H ₂₈ O ₂ C H Calculated value (%) 85.26 6.91 Measured value (%) 85.44 6.79 Representative compounds of the present invention are shown in Table 1.

【table】

【table】

[Table] Typical production methods for starting materials [] will be explained below using reference examples. Reference example 1 2-[4-(cyclopentyloxy)phenyl]
-Synthesis of 2-methylpropyl alcohol Synthesis was performed according to the following sequence. (1) Add 7 g of methyl iodide to a mixture of 10 g of 4-(cyclopentyloxy)acetonitrile, 20 g of potassium hydroxide, 20 g of water, and 2 g of triethylbenzylammonium bromide while keeping the temperature between 80°C and 90°C.
was added dropwise over 1 hour. Then potassium hydroxide 10
g, add 2 g of triethylbenzylammonium bromide and add 7 g of methyl iodide at the same temperature.
was added dropwise over 2 hours. After cooling to room temperature, extraction was performed with toluene. Crude α,α-dimethyl form of 4-(cyclopentyloxy)acetonitrile from toluene layer
11.0g was obtained. (2) A mixture of 11.0 g of the α,α-dimethyl compound synthesized in (1), 80 g of diethylene glycol, 20 g of water, and 20 g of potassium hydroxide was stirred at 130°C to 150°C for 6 hours. After cooling to room temperature, water and toluene were added and stirred. After standing still, the aqueous layer was separated. This was acidified with concentrated hydrochloric acid and then extracted with ether. The ether extracted solution was washed with water and then dried. Ether was distilled off under reduced pressure to obtain 8.5 g of 2-[4-(cyclopentyloxy)phenyl]-2-methylpropionic acid. Melting point: 108-110℃ Elemental analysis value: C ₁₅ H ₂₀ O ₃ C H Calculated value (%) 72.55 8.12 Measured value (%) 72.48 8.08 (3) Add 2.5 g of lithium aluminum hydride to 30 ml of dry tetrahydrofuran and heat under reflux. 2-[4-(cyclopentyloxy)phenyl]-2-methylpropionic acid synthesized in (2) 8.0
g/20 ml of dry tetrahydrofuran solution was added dropwise over 1 hour. After further heating under reflux for 1 hour, ethyl acetate and water were added in that order under ice cooling to decompose excess lithium aluminum hydride. Next, it was extracted with toluene. The obtained toluene solution was washed with water, dried, and the solvent was distilled off under reduced pressure to obtain the desired 2-
[4-(Cyclopentyloxy)phenyl]-2
- 6.5 g of methylpropyl alcohol were obtained. Elemental analysis value: C ₁₅ H ₂₂ O ₂ C H Calculated value (%) 76.88 9.46 Measured value (%) 76.76 9.38 Reference example 2 2-[4-(Cyclopentyloxy)phenyl]
-2-Methylpropyl alcohol Next, it was synthesized according to the sequence. (1) 2,4-bis(4-hydroxyphenyl)-4-methyl-2- in 50ml of dimethyl sulfoxide
Pentene 8.0g, potassium hydroxide 8.0g and water
8.0 g was added thereto, 10 ml of cyclopentyl bromide was added dropwise at 105 to 110° C. over 1 hour, and the mixture was further maintained at the same temperature for 1 hour. After cooling to room temperature, it was poured into water and extracted with toluene. After washing the toluene extract with water and drying, the solvent was distilled off under reduced pressure to obtain the desired 2,
12.8 g of 4-bis[4-(cyclopentyloxy)phenyl]-4-methyl-2-pentene was obtained. (2) 12.8 g of 2,4-bis[4-(cyclopentyloxy)phenyl]-4-methyl- obtained in (1)
Dissolve 2-pentene in 150ml of acetone and heat at 30°C.
50 g of potassium permanganate was added. 30℃
After stirring for 10 hours, 20 ml of ethyl alcohol was added dropwise under cooling to decompose excess potassium permanganate. After continuing to stir for 1 hour, the produced manganese dioxide was filtered, water,
Thoroughly washed with acetone. Acetone was distilled off under reduced pressure, acidified with dilute hydrochloric acid, and extracted with toluene. A dilute aqueous sodium hydroxide solution was added to the obtained toluene solution, and after shaking well, the aqueous layer was separated. The resulting aqueous solution was then acidified with concentrated hydrochloric acid, extracted with toluene, washed with water, and dried. Toluene is distilled off under reduced pressure to obtain the desired 2-
[4-(Cyclopentyloxy)phenyl]-2
- 6.8 g of methylpropionic acid were obtained. (3) Process according to Reference Example 1 (3) to achieve the purpose 2-[4-
(Cyclopentyloxy)phenyl]-2-methylpropyl alcohol was obtained. Other 2-aryl-2-methylpropyl alcohols were synthesized by the methods of Reference Examples 1 and 2 or by known methods. 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 can be formulated with a carrier and diluted as necessary. It is generally applied as follows. 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 into any dosage form such as a fogging agent such as a fogging agent, a non-heated fumigant, a poisonous 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-
Synthetic pyrethroids such as dibromovinyl)-cyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl α-isopropyl-4-chlorophenylacetate, and their various isomers or pyrethrum extract, o,o-diethyl- o-(3-oxo-2-phenyl-2H-pyridazin-6-yl) phosphorothioate (Mitsui Toatsu Chemical registered trademark Offnack), o,o-dimethyl-o-(2,2-dichlorovinyl)-phosphate (DDVP) ), o,o-dimethyl-o-(3-methyl-4-nitrophenyl) phosphorothioate, diazinon, o,o-dimethyl-o-4-cyanophenyl phosphorothioate, o,o-dimethyl-s-[α-( ethoxycarbonyl)benzyl]phosphorodithioate, 2-methoxy-4H-1,
Organophosphorus insecticides such as 3,2-benzodioxaphosphorine-2-sulfide, o-ethyl-o-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, 2-isopropoxyphenyl N-methyl carbamate, other insecticides, acaricides or fungicides, nematicides, herbicides, plant growth regulators, fertilizers, BT agents By mixing it with insect hormones, insect hormones, 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-dicarboximide {MGK-264}, octachlorodipropyl ether {s-421}, iso Its potency can also be increased several times by adding known synergists for pyrethroids, such as bornyl thiocyanoacetate {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 naphthylamine, phenyl-β-naphthylamine, arylamines of condensates of penetidine and acetone, or benzophenone compounds as stabilizers. 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 reference formulation examples in which the compounds of the present invention are used as insecticides and acaricides are shown, but the present invention is not limited to these. All "parts" indicate parts by weight. Reference formulation example 1 Table 1 of the compounds of the present invention, 20 parts of compound numbers 1 to 10 (the same applies hereinafter), Solpol SM-100
(Toho Chemical registered trade name) 20 parts and 60 parts of xylene are stirred and mixed to make an emulsion. Reference 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. Reference Formulation Example 3 Add 5 parts of a surfactant to 20 parts of the compound of the present invention, mix well, add 75 parts of diatomaceous earth, and stir and mix in a Raikai machine to prepare a wettable powder. Reference 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 trademark 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 vessel, and evaporate the acetone to form a powder. Reference Formulation Example 5 2 parts of Ofnatsu (registered trade name of Mitsui Toatsu Chemicals) was added to 0.2 parts of the compound of the present invention, and 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 vessel,
Evaporating acetone creates a powder. Reference 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. Reference Formulation Example 7 An emulsion is obtained by adding 5 parts of Solpol SM-200 (mentioned above) to 0.5 parts of the compound of the present invention and 5 parts of Offnack (mentioned above) and dissolving in 89.5 parts of xylene. Reference formulation example 8 0.4 part of the compound of the present invention, piperonyl butoxide
Mix and dissolve 0.2 parts, 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. Reference Formulation Example 9 When 0.50 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 cm x 1.5 cm and 0.3 mm thick, a hot plate heating fiber fumigation insecticidal composition is obtained. Reference Formulation Example 10 Dissolve 0.5 g of the compound of the present invention in 20 ml of methanol and mix it with an incense stick carrier (3:5 tab flour: lees flour: wood flour).
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. Reference Formulation Example 11 92 parts of clay was mixed with 1 part of the compound of the present invention, 3 parts of Offnatsu (mentioned above), 2 parts of Celogen 7A (Daiichi Kogyo Seiyaku brand name), and 2 parts of Sunextract (Sanyo Kokusaku Pulp Product), and water was added. After granulation and adjusting the particle size to the optimum particle size, it becomes 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 1g.
It is 5g. Next, in order to clarify that the compound of the present invention has excellent insecticidal and acaricidal effects, has low toxicity to warm-blooded animals, and has relatively low toxicity to fish, test examples are provided below. shows. Sample: 20 parts of the compound of the present invention and Solpol SM-
60 parts of xylene was added to 20 parts of 200 (registered trademark of Toho Chemical), 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. 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. (c) Pyrethrin (d) Ofnac (supra) (e) MTMC (supra) (f) Methomyl (s-methyl N-(methylcarbamoyloxy)thioacetamidate) (g) DDVP (supra) (h ) Ortolan (o,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 Reference Formulation Example 1 were prepared at concentrations of 100 and 20 ppm. Sweet potato leaves were immersed in each chemical solution for 10 seconds, air-dried, placed in a plastic cup with a diameter of 10 cm, and 2nd instar larvae of Spodoptera 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 in Table 2 as the average value of three consecutive tests. The test compounds show the compound numbers in Table 1 above.

[Table] Test Example 2 Effect on resistant leafhopper and susceptible leafhopper Rice seedlings (2 to 3 true leaves) were cultivated under water in pots with a diameter of 5 cm, and each test agent was prepared in the same manner as in Test Example 1.
Each pot was treated with 3 ml/pot of chemical solutions having concentrations of 100 and 20 ppm using a sprayer. After air-drying, the seedlings were covered with a wire mesh cylinder, and 10 female adults of each of the resistant leafhopper (native to Nakagawa) and susceptible leafhopper (native to Chigasaki) were released into each pot, and left in a glass greenhouse. 24 hours after treatment, the number of live and dead insects was investigated.
The mortality rate was calculated. The results are shown in Table 3 as the average value of three runs.

[Table] Test Example 3 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 a leaf disk of green bean leaves punched out with a cork borer (15 mm in diameter). A chemical solution with a concentration of 100 ppm of each test drug was applied to the spray tower.
ml applied and processed. 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 in Table 4 as the average value of three series.

[Table] Test Example 4 Fish Toxicity Fill a 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 impact on The results are shown in Table 5.

[Table] Drug concentration test example 5 Toxicity test A prescribed amount of a stock solution (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 investigated after 7 days. , we looked at the effects on mice. The results are shown in Table 6.

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

Claims (1)

[Claims] 1. General formula [] (In the formula, Ar represents a phenyl group, a phenyl group substituted with a phenyl group, a phenoxy group, a lower cycloalkyloxy group, a lower alkoxy lower alkoxy group, a lower alkoxy lower alkylthio group, a lower haloalkoxycarbonyl group, or a tetrahydrofuryloxy group.) A 2-arylpropyl ether derivative represented by: