JPS6121615B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel 2-arylpropyl ether, a method for producing the same, and a low-toxicity insecticide and acaricide containing the compound. More specifically, one of the inventions provides 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-
Concerning methyl propyl ether. 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 [] [In the formula, one group of group A and group B represents a halogen atom, and the other group represents an -O-M group (in the formula,
M represents a hydrogen atom, an alkali or alkaline earth metal atom), or both represent a hydroxyl group. The present invention relates to a method for producing (phenyl)-2-methylpropyl ether. One of the present invention is 3-phenoxybenzyl 2-
The present invention relates to an insecticide and acaricide containing (4-ethoxyphenyl)-2-methylpropyl ether. 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 replaced these insecticides, are widely used. 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 thought that problems such as drug-resistant pests will continue to spread and become more serious in the future. To this day, humans have built up their civilization, and as we seek to maintain an adequate supply of food for further development in the future, there is an urgent need for the emergence of drugs with superior insecticidal activity. be. 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. In other words, it is highly safe, does not leave any residue, decomposes quickly and does not pollute the environment, has high activity against the current problem of chemically resistant pests that are difficult to control, and can be manufactured at low cost. is desired. The present inventors planned to develop an insecticide and acaricide that is low toxicity, low toxicity to fish, and has strong insecticidal power.
As a result of intensive research, we have discovered that 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether has extremely high insecticidal and acaricidal activity, and has excellent immediate and residual effects. The present invention was completed based on the discovery that it has relatively low toxicity not only to humans and livestock, but also to fish, and that it can be put to practical use at a relatively low cost. 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, is one of the representative synthetic pyrethroids, and has the great advantage of not causing any phytotoxicity to plants of the Solanaceae family, such as fuenvalerate. In addition, the compound of the present invention has low toxicity to mammals and has high insecticidal efficacy at low concentrations, so it can be used with substantially high safety for fish.
Not only is it suitable for exterminating pests in rice fields, but it is also suitable for exterminating aquatic pests such as the larvae of mosquitoes and black flies, or for exterminating pests by aircraft spraying in large areas dotted with lakes, marshes, ponds, rivers, etc. can also be used without the risk of killing the fish that live 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, grain storage pests, sanitary pests, house pests, forest pests,
It is highly active as an insecticide and acaricide for aquatic pests, etc., is extremely safe, and can be put to practical use in various dosage forms at low cost. 3-phenoxybenzyl 2-(4-
Ethoxyphenyl)-2-methylpropyl ether is a new compound. The manufacturing method of the present invention will be described in more detail as follows. That is, the general formula [] [in the formula,
When the alcohol of the group A represents an -O-H group] is reacted with the halide of the general formula The desired 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether can be obtained by reaction in a suitable solvent at room temperature to heating. 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, triethylamine, etc., and also deoxidizing agents. Silver oxide can also be used as a metal. 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 dimethyl sulfoxide. Non-proton-donating polar solvents, lower alcohols such as methanol and ethanol, diisopropyl ether, diethyl ether, 1.
Ethers such as 2-dimethoxyethane, tetrahydrofuran, and dioxane, nitriles such as acetonitrile and propionitrile, and ketones such as acetone and diisopropyl ketone can be used. Furthermore, the desired 3-
Phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether can be obtained in good yield. Alcoholate of the general formula [] [where the group A represents a -OM group (in the formula, M is not a hydrogen atom]] and the general formula [] [where the group B represents a halogen atom] When reacting with a halide, 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether can be obtained by carrying out the reaction in the above-mentioned solvent at room temperature or under heating. If the reactivity is poor, it is also suitable to add a catalytic amount of potassium iodide, copper iodide, etc. A halide of the general formula [] [where group A represents a halogen atom] and a halide of the general formula [] [where the group B represents a -OM group (in the formula, M represents the above meaning)] When reacting with an alcohol or an alcoholate in [case], it can be carried out in the same manner as described above. In particular, the halide of the general formula [] [in the formula, when group A represents a halogen atom] and the general formula []
(wherein the group B represents -OH) is reacted in the presence of an aprotic polar solvent, preferably dimethyl sulfoxide or sulfolane, and in the presence of a base as a deoxidizing agent.
The desired 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether can be obtained in good yield by the reaction under heating. Alcohol of general formula [] [in the formula, when group A is a hydroxyl group] and general formula [] [in the formula,
When group B is a hydroxyl group], a dehydration reaction is carried out in the presence of a catalyst to obtain 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether. I can do it. 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 catalysts (alumina-titanium oxide, etc.), dimethyl sulfoxide, alumina, sulfamide, ion exchange resins, etc. can also be used as dehydration catalysts. Benzene if necessary
It is preferable to carry out the reaction in an inert solvent that is azeotropic with water, such as toluene, while removing the 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. 3-phenoxybenzyl by reacting with alcohol]
2-(4-ethoxyphenyl)-2-methylpropyl ether can also be obtained. 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-dimethoxyethane, dioxane, and tetrahydrofuran, aproton-donating polar solvents such as dimethylformamide, hexamethylphosphonic acid triamide, and dimethyl sulfoxide, acetone, methyl ethyl ketone, and cyclohexanone. Examples include ketones such as. Others, 3-phenoxybenzyl 2-(4-
As a method for producing ethoxyphenyl)-2-methylpropyl ether, the general formula [ ] [wherein the group A
A method of reacting a metal alcoholate or sulfonic acid ester of an alcohol with a metal alcoholate or a sulfonic acid ester of the alcohol represented by the general formula [] [in which the group B represents a hydroxyl group], When 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 prepared analogously to known methods described in the literature. That is, the alcohol represented by the general formula [] [where the group A represents a hydroxyl group] is
For example, it can be obtained by alkylating the corresponding 4-ethoxyphenylacetonitrile with methyl halide, then hydrolyzing the obtained nitrile to convert it into the corresponding carboxylic acid, and reducing the carboxylic acid. It is also obtained by converting a halide obtained by adding methallyl halide to 4-ethoxybenzene (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. References Roczniki Chem., 39 (9), 1223
(1965) (Pol) [Chemical Abstract 64 ,
12595, h (1966)] Produced according to the route (1) below. [In formula [], group A is a halogen atom] References Chem, Ber., 94 , 2609 (1961) Reference J.Am.Chem.Soc., 65 , 1469 (1943) Also, the alcohol of the general formula [] [where the 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 of the general formula [] [where the group A represents an -OM group and M is not a hydrogen atom] can be prepared by a conventional method, for example, with a metal hydride such as sodium hydride and the general formula [] [In the formula, when group A represents an -OM group and M is a hydrogen atom]
It can be easily obtained by reacting alcohol. Alcohols of the general formula [] [where group B is a hydroxyl group] are known as alcohol components of synthetic pyrethroids. Next, the 3-phenoxybenzyl 2- of the present invention
The method for producing (4-ethoxyphenyl)-2-methylpropyl ether will be described in more detail below with reference to synthesis examples. Synthesis Example 1 (Etherification Method A) Add 0.90 g of sodium hydride (60% in oil) to 20 ml of dry acetonitrile, then add 3.0 g of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol/10 ml of dry acetonitrile. The solution was added dropwise at 50°C. After heating under reflux for 30 minutes, a solution of 4.8 g of 3-phenoxybenzyl bromide/10 ml of dry acetonitrile 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. The toluene extract was washed with saturated brine and dried over anhydrous sodium sulfate. The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography on 150 g of silica gel [developing solvent: benzene:n-hexane (2:3)] to obtain 3-phenoxybenzyl 2-(4). -ethoxyphenyl)-2-methylpropyl ether 4.2
I got g. ⁿ²⁰ . ² _D 1.5732 ν ^film _nax 1595, 1525, 1495, 1260, 1225, 1195
,
1110, 1055, 830, 700cm ^-1 δ ^CCl4 _TMS (ppm) 1.29 (s.6H), 1.37 (t, J
=6.9
Hz, 3H), 3.32 (s, 2H), 3.93 (q, J=6.9
Hz, 2H), 4.38 (s, 2H), 6.6-7.35 (m,
13H) Elemental analysis results C ₂₅ H ₂₈ O ₃ Calculated value (%) C; 79.76, H; 7.50 Actual value (%) C; 79.97, H; 7.34 3-Phenoxybenzyl 2-(4) obtained above
-ethoxyphenyl)-2-methylpropyl ether solidified upon standing at room temperature for an extended period of time. The melting point is
The temperature was 35-38℃. Sludge this with methanol, filter, wash,
After drying, sludge with n-hexane, filtration, washing and drying, white crystals with a melting point of 36.4-38°C were obtained. Synthesis Example 2 (Etherification Method B) Sodium hydride (60% in
After adding 0.63 g of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol to this
g/25% DMF-Toluene 10ml solution was heated under reflux.
It was added dropwise over 15 minutes. After continuing stirring for 10 minutes, 3-phenoxybenzyl bromide 3.3
g/25% DMF-toluene 10ml solution was added dropwise over 20 minutes. After further heating under reflux for 1 hour, the reaction mixture was cooled to room temperature and poured into water. After extraction with toluene and washing the toluene extract with water, it was dried over anhydrous sodium sulfate. The oil obtained by distilling toluene off under reduced pressure was purified by column chromatography [100 ml of silica gel, benzene:n-hexane (2:3)] to obtain 3.0 g of the desired pure ether. Synthesis Example 3 (Etherification Method C) 30g of 50% NaOH aqueous solution, 6.3g of 2-(4-ethoxyphenyl)-2methylpropyl alcohol, 3
-7.6 g of phenoxybenzyl 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 the reaction mixture to room temperature, water was added, extracted with toluene, and washed with water. After drying the toluene extract over anhydrous sodium sulfate, the toluene was distilled off under reduced pressure, and the resulting crude ether was subjected to column chromatography [silica gel developing solvent: benzene: n-hexane (2:
3)] to obtain 10.0 g of the desired ether. Synthesis Example 4 (Etherification method D) 0.50 p-toluenesulfonic acid in 50 ml of toluene
g, 2.5 g of 3-phenoxybenzyl alcohol,
2.5 g of 2-(4-ethoxyphenyl)-2-methylpropyl 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 purified by column chromatography [silica gel, developing solvent: benzene:n-hexane (2:3)] to obtain the desired ether. Synthesis Example 5 (Etherification Method E) Mixing of 1.8 g of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol, 2.4 g of 3-phenoxybenzyl chloride, 20 g of 50% NaOH, and 0.3 g of triethylbenzylammonium bromide. The liquid was stirred at 50°C for 2 hours. After the reaction mixture was cooled to room temperature, water was added and extracted with benzene. The benzene extract was washed with dilute hydrochloric acid, then water, and dried. The crude ether obtained by distilling off benzene under reduced pressure was subjected to column chromatography (silica gel 80
g, developing solvent: benzene-n-hexane, 2:
3) to obtain 2.8 g of the desired ether. Synthesis Example 6 (Etherification Method F) 4-ethoxyneofyl chloride 8.9g, 3
- 8.5 g of phenoxybenzyl alcohol, 3.9 g of 45% caustic soda and dimethyl sulfoxide
48g was 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. After cooling the reaction solution to room temperature, pour it into water.
After extraction with benzene, the benzene extract was washed with water and then dried. The crude ether obtained by distilling off benzene under reduced pressure was separated and purified by column chromatography (300 g of silica gel, developing solvent: benzene:n-hexane 2:3) to obtain 10.3 g of the desired ether. The method for producing alcohol and halide as starting materials [] will be explained in detail below using synthetic reference examples. Synthesis Reference Example 1 Synthesis of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol (4-ethoxyneofyl alcohol) Synthesis was performed according to the following sequence. (1) Synthesis of 2-(4-ethoxyphenyl)-2methylpropionitrile 280 g of 4-ethoxybenzyl nitrile, 80 g of triethylbenzylammonium bromide,
When 750 g of potassium hydroxide and 750 g of water were charged into two separable flasks and stirring was started, the internal temperature rose to about 85-90°. This includes methyl iodide
180 ml (approximately 410 g) was added dropwise over 1.5 hours. Stirring was then continued for an additional 7 hours at 80-90°C. After cooling the reaction solution to room temperature, it was extracted with 500 ml of benzene, and the benzene extract was washed with dilute hydrochloric acid and water in that order, and then dried over anhydrous sodium sulfate. Benzene was distilled off under reduced pressure to obtain 311 g of crude 2-(4-ethoxyphenyl)propionitrile. Crude 2-(4-ethoxyphenyl) obtained above
311 g of propionitrile, 110 g of triethylbenzylammonium bromide, 800 g of potassium hydroxide, and 800 g of water were charged into two separable flasks and stirred. Next, 180 ml (approximately 410 g) of methyl iodide was added dropwise at 85 to 90° C. over 1.5 hours.
After 3.5 hours had passed after the completion of the dropping, 300 g of potassium hydroxide was additionally charged. After a further 5 hours, 50 ml (approximately 114 g) of methyl iodide was added. The reaction was further continued at the same temperature for 2 hours. The crude 2-(4-ethoxyphenyl)-2 was then treated in the same manner as in the synthesis of 2-(4-ethoxyphenyl)propionitrile.
-340 g of methylpropionitrile were obtained. The product was purified by distillation under reduced pressure to obtain 275 g of the desired product. (111～
112℃/0.60~0.55mmHg). (2) Synthesis of 2-(4-ethoxyphenyl)-2-methylpropionic acid 275 g of 2-(4-ethoxyphenyl)-2-methylpropionic acid, 850 g of potassium hydroxide,
700 ml of water and 2000 ml of ethylene glycol were reacted for 8 hours under reflux at 121 to 126° C. with stirring. After the reaction mixture was cooled to room temperature, it was poured into 2 to 3 portions of water, and the neutral portion was removed with benzene. The aqueous layer was adjusted to pH 2 or less with concentrated hydrochloric acid and extracted with benzene. The benzene extract was washed with water, dried over anhydrous sodium sulfate, and after distilling off the benzene, it was recrystallized from n-hexane. mp80.5~82.5℃ 2-
240 g of (4-ethoxyphenyl)-2-methylpropionic acid was obtained. (3) Synthesis of ethyl 2-(4-ethoxyphenyl)-2-methylpropionate 240 g of the carboxylic acid obtained in (2) was mixed with 400 ml of benzene,
After dissolving in 200 ml of ethanol, 25 ml of concentrated sulfuric acid is added and the azeotrope of benzene-ethanol-water is removed from the system under reflux. At this time, a mixed solution of 400 ml of benzene and 200 ml of ethanol was added dropwise to the reactor over a period of 6 hours. After cooling the reaction mixture to room temperature, water was added and the benzene layer was separated. The obtained benzene solution was washed with water until it became neutral, and then dried. Benzene was distilled off under reduced pressure to obtain 264 g of the desired ester. (4) Synthesis of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol Add 35 g of lithium aluminum hydride to 400 ml of dry tetrahydrofuran and add (3)
264 g of the ester obtained above was added dropwise while keeping the temperature below 30°C. After the completion of dropping the ester, the mixture was refluxed for 30 minutes. Next, in order to decompose excess lithium aluminum hydride, 30 ml of ethyl acetate was added dropwise under ice cooling. When heat generation and foaming were no longer observed, water was added to completely decompose the lithium aluminum hydride. After removing the generated precipitate under reduced pressure, tetrahydrofuran was distilled off under reduced pressure. Extraction was performed with 300 ml of benzene, and the extract was washed with water and dried. Benzene was distilled off under reduced pressure, and 2-(4-ethoxyphenyl)-2-
213 g of methylpropyl alcohol was obtained. mp; 42.0-43.5℃ ν ^KBr _nax ; 3400, 1620, 1520, 1255, 1195, 1050
,
830cm ^-1 Synthesis reference example 2 Synthesis of 4-ethoxyneofyl chloride Equipped with stirrer, Dimroth, thermometer and dropping funnel
After adding 120 g of concentrated sulfuric acid to a 500 ml flask, 200 g of phenetol was added dropwise while maintaining the temperature at 5°C. 0℃
While maintaining the temperature at ~10°C, a mixed solution of 90 g of methallyl chloride/165 g of phenetol was added dropwise over 10 hours.
Then, after keeping at 25°C for 15 hours, it was poured into ice water. After separating the organic layer, it was thoroughly washed in the order of dilute aqueous sodium hydroxide solution and water. After drying with anhydrous sodium sulfate, crude 4-
16 g of ethoxyneofyl chloride was obtained (114
℃/2.0mmHg to 116.5℃/1.7mmHg). δ ^CCl4 (ppm) 1.39 (s, 6H), 1.3-1.6 (m,
3H), 3.51 (s, 2H), 4.05 (q, J=6.9Hz,
2H), 4.05 (q, J=6.9Hz, 2H), 6.6-7.3
(m, 4H) Reference: Chem, Ber., 94, 2609 (1961) Next, the names of specific pests to which the insecticide and acaricide of the present invention can be applied are listed [scientific name - (Japanese name) - English name]. 1 Hemiptera Nephotettix cincticeps Uhler Green rice leafhopper Sogata furcifera Horva'th White-backed rice planthopper Nilaparvata lugens Sta゜l Brown rice planthopper Laodelphax striatellus Falle'n Small brown planthopper Eurydema rugosum Motschulsky Cabbage bug Eysarcoris parvus Uhler Whitespotted spined bug Halyomorpha mista Uhler Brown-marmorated stink bug Lagynotomus elongatus Dallas Rice stink bug Nezara viridula Linne′ Southern green stink bug Cletus trigonns Thunberg′ Slender rice bug Stephanitis nashi Esaki et, Takeya Japanese pear lace bug Stephanitis pyrioides Scott Azalea lace bug Psylla pyrisuga Fo¨rster
Pear sucker Psylla mali Schmidberger Apple sucker Aleurolobus taonabae Kuwana Grape whitefly Dialeurodes citri Ashmead Citrus whitefly Trialeurodes vaporariorum Westwood Greenhouse whitefly Aphis gossypii Glover
Cotton aphid Brevicoryne, brassicae Linne′ 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 Spu´lerina astaurcta Meyrick Pear bark miner Phyllonorycter ringoneella Matsumura Apple leafminer Plutella xylostella Linne′
Diamond back moth Promalactis inopisema Butler
Cotton seedworm Adoxophyes orana Fischer von
Ro¨slerstamm Smaller
tea tortrix Bactra furfurana Haworth Mat rush worm Leguminivora glycinivorella Matsumura
Soybean pod borer Cnaphalocrocis medinalis Guene′e Rice leaf roller Etiella zinckenella Treitschke Lima-bean pod borer Ostrinia furnacalis Gueue′e Oriental corn borer Pleuroptya derogata Fabricius Cotton leaf roller Hyphantria cunea DruryFall webworm Abraxas miranda ButlerMagpie moth Lymantria dispar japonica Motschulsky
Gypsy moth Phalera fiavescens Bremer etGreyCherry caterpiller Agrotis segetum Denis et Schiffer mu¨ller
Cutworm Helicoverpa armigera Hu¨bner Cotton, boll worm Pseudaletia separata Walker Armyworm Mamestra brassicae Linne′
Cabbage armyworm Plusia nigrisigna Walker Beet semi-looper Spodoptera litura Fablicius Common cutworm Parnara guttata Bremer et Gray Rice skipper Pieris rapae crucivora Boisduval Common cabbageworm Chilo suppressalis Walker
Rice stem borer 3 Coleoptera Melanotus fortnumi Cande'ze Sweetpotato wirewerm Anthrenus verbasci Linne' Varied carpet beetle Tenebroides mauritanicus Linne' Cadelle Lyctus brunneus Stephens powder post beetle Henosepilachna vigintioctopunctata
Fablicius 28−
spotted lady beetle Monochamus alternatus HopeJapanese pine sawyer Striped flea beetle Callosobruchus chinensis Linne′ Azuki bean, weevil Echinocnemis squameus Billberg Rice plant weevil Sitophilus oryzae Linne′
Rice weevil Apoderus erythrogaster Vollenhoven 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 Azalea argid sawfly Arge pagana Panzer
Rose argid sawfly 5 Diptera Tipura aino Alexander Rice crane fly Culex pipiens fatigans Wiedemann House mosquito Aedes aegypti Linne′
Yellow−fever mosquito Asphondylia sp.
Soybean pod gall midge Hylemya antiqua Meigen (onion fly)
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 leafmier 6 Siphonaptera Pulex irritans Linne′ )Human
flea Xenopsylla cheopis Rothschild Tropical rat flea Ctenocephalides canis Curtis
Dog flea 7 Thysanoptera Scirtothrips dorsalis Hood, Yellow tea trips Thrips tabaci Lindeman Onion thrips Chloethrips oryzae Williams Rice thrips 8 Anoplura Pediculus humanus corporis De Geer Body louse Phthirus pubis Linne′ Crab
louseHaematopinus eurysternus Nitzsh) Short-nosed cattle louce 9 Psocoptera Trogium pulsatsrium Linne′ large pale booklouse Liposcelis bostrychophilus Badonnel Flattened booklice 10 Orthoptera Gryllotalpa africana palisot de Beauvois
(Mole cricket) African mole cricket Locusta migratoria danica Linne′ (Tonosama battuta) Asiatic locust Oxya yezoensis Shiraki (Kobanei locust)
Short-winged rice grass hopper 11 Dictyoptera Blattella germanica Linne′ German cockroach Periplaneta fuliginosa Serville Smoky-brown cockroach 12 Acarina Boophilus microplus Canestrini Bull tick Polyphagotarsonemus latus Banks Broad mite Panonychus citri McGregor Citrus red mite Tetranychus cinnabarinus Boisduval Carmine Spider mite Tetranychus urticae Koch
Two-spotted spider mite Rhizoglyphus enhinophus 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 using methods well known in the art in accordance with general agricultural chemicals, without requiring 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 for focking, a non-heating fumigant, a poisonous bait, etc., and can be used for various purposes depending on the purpose of each. Furthermore, other physiologically active substances, such as allethrin [d·l-(3-allyl-2-methyl-2-cyclopenten-4-one-1-yl)chrysanthemate], N-(chrysansemoylmethyl)-3・４・
5,6-tetrahydrophthalimide, 5-benzyl-3-furylmethyl chrysansemate, 3-
Phenoxybenzyl chrysanthemate, 5-propargyl furfuryl chrysanthemate, other known cyclopropane carboxylic acid esters, 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane -1-carboxylate, 3-phenoxy-α-cyanobenzyl 3-(2,2-dichlorovinyl)-2,2
-dimethylcyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl 3-
(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl α-isopropyl-
Synthetic pyrethroids such as 4-chlorophenylacetate and their various isomers or pyrethyl extracts, 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-1,3,2-benzodioxaphospho Organophosphorus insecticides such as phosphorus-2-sulfide, o-ethyl-o-4-cyanophenyl phenylphosphonothioate, 1-naphthyl-
N-methyl carbamate (NAC), m-tolyl-
N-Methyl carbamate (MTMC), 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-dimethylcarbamate (pyrimer), 3,4
-dimethylphenyl N-methylcarbamate, 2
- Carbamate insecticides such as isopropoxyphenyl N-methyl carbamate, other insecticides, acaricides or fungicides, nematicides, herbicides, plant growth regulators, fertilizers, BT agents, insect hormone agents, By mixing it with other agricultural chemicals, etc., it is possible to create a multipurpose composition with even greater efficacy, and a synergistic effect can also be expected. Further, 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 {safloxane}, N-(2-ethylhexyl)-picyclo(2,2,1)hept-5-ene-2,3-
By adding known synergists for pyrethroids, such as dicarboximide {MGK-264}, octachlorodipropyl ether {s-421}, and isobornyl thiocyanoacetate {Garnite}, its potency can be increased several times. You can also. The compound of the present invention has high stability against light, heat, oxidation, etc., but if necessary, antioxidants or ultraviolet absorbers such as BHT (2,6-di-tert-butyl-4-methylphenol), BHA Phenol derivatives such as (butyl-hydroxyanisole),
Bis-phenol derivatives, also phenyl-α-naphthylamine, phenyl-β-naphthylamine,
By adding an appropriate amount of arylamines such as a condensate of phenetidine and acetone or benzophenone compounds as a stabilizer, a composition with more stable effects can be obtained. 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 20 parts of the compound of the present invention, 20 parts of Solpol SM-100 (a mixture of nonionic surfactant and anionic surfactant, trade name of Toho Chemical Co., Ltd.), and 60 parts of xylol were stirred and mixed to form an emulsion. do. 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 then add 0.2 parts of PAP (isopropyl acid phosphate, registered trademark of Nihon Kagaku Kogyo Co., Ltd., physical property improver) to 10 parts of acetone. Dissolve, add 97.6 parts of powder clay, stir and mix in a Raikai vessel, and evaporate the acetone to form a powder. Formulation Example 5 Add 2 parts of Offnack (mentioned above) to 0.2 parts of the compound of the present invention, further add 0.2 parts of PAP (mentioned above), dissolve in 10 parts of acetone, add 97.6 parts of powder clay, and stir in a Raikai vessel. Mix and evaporate the acetone to form a powder. Formulation Example 6 Add 0.5 parts of piperonyl butoxide (mentioned above) to 0.1 part of the compound of the present invention, dissolve in white kerosene, and add 0.1 part of the compound of the present invention to 100%
%, it becomes an oil agent. Formulation Example 7 Solpol SM-200 (Solpol SM-
Add 5 parts of (same as 100) and dissolve in 89.5 parts of xylene to form an emulsion. Formulation Example 8 Compound of the present invention, 0.4 parts, piperonyl butoxide (above) 20 parts, xylol 6 parts, deodorized kerosene 7.6 parts
After mixing and dissolving 84 parts of the propellant (liquefied petroleum gas) and filling it into an aerosol container, attaching the valve part and pressurizing 84 parts of propellant (liquefied petroleum gas) through the valve part, it becomes 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 cm 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 a carrier for incense sticks (Tab flour: Leek flour; Wood flour: 3:5:
Stir and mix evenly with 99.5 parts of (mixed at a ratio of 1 part)
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 Offnatsu (mentioned above), 2 parts of Celogen 7A (carboxymethyl cellulose, trade name of Daiichi Kogyo Seiyaku Co., Ltd.), Sunextract (ligninsulfonic acid-Na salt, Sanyo Kokusaku Pulp Co., Ltd.) (Product name) 2 parts and 92 parts of clay are mixed, water is added and granulated, and the particles are sized to the optimum particle size to form granules. When applying the compound of the present invention, the amount of active ingredient to be applied is generally 300 g to 1 g, preferably 100 g to 2 g per 10 ares. 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 Sorbol SM-
200 (Toho Chemical registered trademark name) 20 parts xylol 60
of the mixture 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 Pesticid 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 N-(methylcarbamoyloxy)thioacetamidate) (g) DDVP (Supra) (h) Ortolan (os-dimethyl N-acetyl phosphoramidothiolate) (i) Permethrin [3-phenoxybenzyl 2.
2-Dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylate] Test Example 1 Effect on Spodoptera spp. Emulsions of each test compound prepared according to Formulation Example 1 were adjusted to concentrations of 100 and 20 ppm. do. 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 the second 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.

[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 pre-prepared plastic cups, 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 of local application on Spodoptera trifoliata Each test compound was dissolved in acetone, and 0.25 μg/g of body weight was applied to 3rd instar larvae of Spodoptera pruriens using a micro-dose local application device. The number of live and dead insects was investigated 24 hours after treatment. The results are shown as the average value of three consecutive runs.

[Table] Test Example 4 Effect on resistant leafhopper and susceptible leafhopper Rice seedlings (2 to 3 true leaves) were hydroponically cultured in pots with a diameter of 5 cm, and 100% of each test chemical prepared in the same manner as Test Example 1 was used. and 3 ml/pot of each drug solution with a concentration of 20 ppm was applied using a sprayer. After air-drying, the seedlings were covered with a wire mesh cylinder, and resistant leafhoppers (from Nakagawa) and susceptible leafhoppers (from Chigasaki) 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. The results are shown as the average value of three consecutive runs.

[Table] Test Example 5 Effect of water surface application on leafhopper Paddy rice at the 3-leaf stage was transplanted into a 1/10000a pot and allowed to take root. While keeping the water depth at 2 cm, 1% granules of each compound were prepared as a trial, and 5 g of the active ingredient was applied per 10 acres. The pot was covered with a wire mesh cylinder, and male adult leafhoppers (from Chigasaki) were released. After 24 hours, the number of living and dead insects was examined to determine the mortality rate. The results are shown as the average value of three consecutive runs.

[Table] Test Example 6 Effect on diamondback moth A plastic cup was covered with citrus leaves and 10 third instar diamondback moth larvae were released. 3 ml of each test chemical solution prepared in the same manner as in Test Example 1 at concentrations of 100 and 20 ppm was sprayed per cup using a spray tower. 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. The results are shown as the average value of three series.

[Table] Test Example 7 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.
Each pot was treated with 10 ml of chemical solutions at concentrations of 100 ppm, 20 ppm, and 4 ppm using a spray gun. After treatment, the plants were left in a glass greenhouse, and the number of live insects was counted 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] Test Example 8 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 (15 mm in diameter).
3ml of 100ppm concentration of each test drug in a spray tower
I dealt with it. 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] Test Example 9 Effect on German cockroaches Each test compound was applied to the bottom of a waist-high shear dish with a diameter of 9 cm and a height of 9 cm at doses of 50 mg/m ² , 10 mg/m ² , 1 mg/m ² and 0.5
treated with mg/ ^m2 . 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] Test example 10 Fish toxicity Fill a water tank with width 60cm, length 30cm, and height 40cm.
After releasing 10 common carp fish with a body length of about 5 cm and allowing them to acclimate, each test chemical was added to the water at a concentration of 10.1 ppm, 0.1 ppm, etc., and after 48 hours, the number of live and dead fish was investigated.
We looked at the effects on fish.

[Table] Example of drug concentration test that causes death 11 Toxicity test A prescribed amount of the 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 calculated after 7 days. We investigated the effect on mice.

[Table] *Half of the animals tested died.
The amount of the compound of the present invention that is highly effective against target pests,
It is clear that it has relatively low toxicity to fish, but in order to further clarify this characteristic, a fish toxicity safety factor was determined from the results of fish toxicity and insecticidal tests. Fish toxicity safety factor = fish toxicity (TLm ₄₈ ppm) / drug concentration in water (LC ₅₀ ppm) Female adult susceptible leafhoppers (Chigasaki) were tested at various concentrations according to Test Example 4,
Determine the median lethal dose (LC ₅₀ ppm value) from the mortality rate of each triplicate. The concentration in water is based on the assumption that a solution with a concentration equivalent to the sprayed LC ₅₀ (ppm) value is sprayed at 100 times per 10 ares into a rice field flooded to a depth of 5 cm, and all of this is mixed into the water. For example, with the compound of the present invention, the amount of water in 10 ares at a depth of 5 cm is 50 tons, and there is 100 tons per 10 ares.
If the amount of active ingredient with LC ₅₀ (ppm) value is sprayed, the drug concentration in water will be 0.0102 ppm. On the other hand, since the fish toxicity TLm ₄₈ (ppm) for carp is >0.1 ppm, the fish toxicity safety factor can be calculated by dividing the fish toxicity TLm ₄₈ (ppm) by the drug concentration in water. In this case, the value will be 9.8 or higher.

[Table] The compound of the present invention is 70 times safer than the comparative compound. As is clear from the results of the above drug efficacy tests and toxicity tests, the compounds of the present invention have superior insecticidal activity compared to comparative compounds, are extremely low in toxicity to warm-blooded animals, and are also highly effective against fish. It has the characteristics of being less toxic and substantially safer than synthetic pyrethroids.

Claims (1)

[Claims] 1 3-Phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether. 2 A compound represented by the general formula [] is a compound represented by the general formula [] [In the formula, one group of group A and group B represents a halogen atom, and the other group represents an -O-M group (in the formula,
M represents a hydrogen atom, an alkali or alkaline earth metal atom), or both represent a hydroxyl group. Method for producing phenyl)-2-methylpropyl ether. 3 In the general formula [], the group A is an -OM group (in the formula, M represents the above meaning), and in the general formula [], the group B is a halogen atom, The manufacturing method according to claim 2. 4 In general formula [], when group A is a halogen atom and in general formula [], group B is a hydroxyl group, in the presence of dimethyl sulfoxide or sulfolane, a compound represented by general formula [] and general formula The manufacturing method according to claim 2, characterized in that a compound represented by [ ] is reacted. 5 In general formula [] and general formula [],
3. The method according to claim 2, wherein both group A and group B are hydroxyl groups. 6 An insecticide and acaricide characterized by containing 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether.