JPH045008B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel aromatic alkane compound, a method for producing the same, and an insecticide containing the same as an active ingredient.
Regarding acaricides. The aromatic alkane compound of the present invention has low toxicity to warm-blooded animals and fish, and extremely high insecticidal and acaricidal activity. [Prior art] Conventionally, as agricultural and horticultural or epidemic prevention insecticides,
Many organochlorine insecticides such as DDT and BHC, organophosphorus insecticides such as parathion and malathion, and carbamate insecticides such as carbaryl and methomyl have been developed and are used in large quantities to control agricultural, horticultural, and sanitary pests. It has made a major contribution to the prevention of agricultural crops. However, in recent years, consideration has been given to the use of these insecticides from the viewpoint of pollution problems such as environmental pollution, and safety such as residual and accumulation. Furthermore, some of these products have developed resistant pests due to long-term use. With the above points in mind, pyrethroid compounds have been developed and put into practical use because they generally have low toxicity, are easily degradable in the environment, have little persistence, and their decomposition products are nontoxic. ing. However, the pyrethroid compounds that have already been put into practical use have the drawback of high toxicity to fish. Although pyrethroids with low fish toxicity have been studied and reported, there is an undeniable tendency for insecticidal activity to decrease as fish toxicity safety increases. [Problems to be Solved by the Invention] An object of the present invention is to provide a highly active insecticide and acaricide that overcomes the above drawbacks and is highly safe for warm-blooded animals and fish. [Means and actions for solving the problem] The present inventors have conducted extensive research with the aim of developing insecticides and acaricides that overcome these drawbacks and are highly safe for warm-blooded animals and fish. As a result, it was discovered that a novel aromatic alkane compound represented by the following general formula () is safe to warm-blooded animals, has low toxicity to fish, and has high insecticidal and acaricidal activity, and the present invention has been completed. It came to this. That is, the present invention is based on the formula () It is an aromatic alkane compound represented by The present invention also relates to an insecticidal and acaricidal composition characterized by containing an aromatic alkane compound represented by the formula () as an active ingredient. Conventional pyrethroid compounds are generally cyclopropanecarboxylic acid esters, and various attempts have been made to convert each segment, and it has been found that even when cyclopropanecarboxylic acid is replaced with substituted acetic acid, it exhibits high insecticidal activity ( M. Elliott et al, Chem.
Soc.Reviews, 1978, 473, JP-A-49-26425, JP-A-49-126826). Various attempts have been made to convert ester bonds, and in recent years it has been reported that compounds represented by oxime ether bonds exhibit high insecticidal activity (Japanese Patent Application Laid-Open No. 103449-1989).
Publication No. 141740, Japanese Patent Application Laid-Open No. 1983-141740
Publication No. 138532). Furthermore, it has been reported that compounds having an ether bond exhibit high insecticidal activity (West German Published Patent Application No. 3117510). The compound of the present invention has a previously unknown -CH ₂ CH ₂ - bond in place of the ester bond -COO-, and has an active structure different from that of conventional agricultural chemicals. It is toxic and has high insecticidal and acaricidal activity. The method for producing the compound of the present invention is based on the formula () aldehyde and the formula () The compound of -70 to
React at 100℃, formula () The compound () can be obtained, which can then be reduced with hydrogen to obtain the compound (). Ether, dichloromethane, THF, DMSO, HMPA, benzene, alcohol, dimethyl cellosolve, etc. can be used as the inert solvent. A compound of formula () is a compound of formula () It can be easily obtained by reacting with (C ₂ H ₅ O) ₃ P. The compound of formula () can also be produced by reducing the corresponding nitrile or acid chloride according to methods known in the literature. The compound of the present invention is highly effective against sanitary pests such as flies, mosquitoes, and cockroaches, as well as pesticide pests such as planthoppers, leafhoppers, armyworms, diamondback moths, leafhoppers, aphids, caterpillars, and spider mites, especially against black leafhoppers. It is extremely effective in controlling insects that kill insects such as white mites, white-spotted moths, and brown elephants, 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 insect pests and causes them to die, but also has repellent properties and has the effect of repelling insect pests from the host. It has the great advantage of not causing any phytotoxicity to nightshade plants. In addition, it has low toxicity to mammals. The compound of the present invention is also highly safe for fish, and is suitable not only for exterminating pests in rice fields, but also for exterminating aquatic pests such as mosquitoes and black fly larvae, and for exterminating insects in lakes, marshes, etc. Even when using aircraft to exterminate pests in large areas dotted with 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, grain storage pests, sanitary pests, house pests, forest pests,
Furthermore, 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. Next, the names of specific pests to which the insecticide and acaricide of the present invention can be applied are listed [Japanese name - English name]. 1 Hemiptera (Hemiptera) Green rice leafhopper White-backed rice plant
hopper Brown rice planthopper Small brown planthopper Cabbage bug Whitespotted spined
bug Brown-marmorated stink
bug Rice stink bug Southern green stink
bug Slender rice bug Japanese pear lace bug Azalea lace bug Pear sucker Apple sucker Grape whitefly Citrus whitefly Greenhouse whitefly Cotton aphid Cabbage aphid Green peach aphid peach aphid millet Corn leaf aphid Cottonycushion scale citrus mealybug arrowhemd scale 2 Lepidoptera Mulberry bagworm Pear bark miner Apple leafminer Diamond back moth Cotton seedworm Smaller tea tortrix Igusasinmushiga Mat rush worm Soybean pod borer Rice leaf roller Lima-bean pod
borer Oriental corn borer Cotton leaf roller Fall webworm Magpie moth Gypsy moth Cherry caterpillar Cutworm Cotton boll worm Armyworm Cabbage armyworm Beat semi-looper mon cutworm Rice skipper Common cabbageworm Rice stem borer 3 Coleoptera (Coleoptera) Sweetpotato
wireworm Varied carpet beetle Cadelle Powder post beetle 28−spotted lady
beetle Japanese pine sawyer Grape borer Cucurbit leaf beetle Rice leaf beetle Striped flea beetle Azuki bean weevil Rice plant weevil Rice weevil Rice weevil Small black−cut weevil Peach curculio Cupreous chafer Japanese beetle 4 Hymenoptera Cabbage sawfly Azalea argid sawfly Rose argid sawfly 5 Diptera Rice crane fly House mosquito Yellow-fever mosquito soybean Soybean pod gall midge Onion maggot Seep corn maggot House fly Melon fly Rice stem maggot Rice leafminer 6 Siphonaptera (Cardoptera) Human flea Tropical rat flea Dog flea 7 Thysanoptera ( Onion thrips Rice thrips 8 Anoplura Body louse Crab louse Short-nosed cattle louce 9 Psocoptera Larger pale booklo use Flattened booklice 10 Crthoptera (Orthoptera) African mole cricket Asian locust Short-winged rice grass
hopper 11 Dictyoptera German cockroach Smoky-brown cockroach 12 Acarina Bull tick Broad mite Citrus red mite Carmine spider mite Two-spotted spider mite Bulb mite Book When the invented compound is actually applied, 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. When formulating the compound of the present invention, no special conditions are required;
Emulsions, wettable powders, powders, granules, fine granules, oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.),
It can be prepared in any form, such as a fogging agent such as a fogging agent, a non-heated fumigation agent, or a poisonous bait, and can be used for various purposes depending on the purpose. Furthermore, the compounds of the present invention may contain other physiologically active substances, such as allethrin, N-(chrysansemoylmethyl)-
3,4,5,6-tetrahydrophthalimide,
5-benzyl-3-furylmethyl chrysanthemate, 3-phenoxybenzyl chrysanthemate,
5-propylgyl furfuryl 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 insect repellent extract, 0,0-diethyl-0-
(3-oxo-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 ate, 0,0-dimethyl-
S-[α-(ethoxycarbonyl)benzyl]phosphorodithioate, 2-methoxy-4H-1,3,
Organophosphorus insecticides such as 2-benzodioxaphosphorine-2-sulfide and 0-ethyl-0-4-cyanophenyl phenylphosphonothioate;
1-Naphthyl-N-methylcarbamate (NAC), m-tolyl-N-methylcarbamate (MTMC), 2-dimethylamino-5,6-dimethylpyridin-4-yl-dimethylcarbamate (pyrimer), 3,4- Dimethylphenyl N-methylcarbamate, 2-isopropoxyphenyl N
- Carbamate insecticides such as methyl carbamate, 3-phenoxybenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl) 2-methylpropyl ether , 3-
Phenoxybenzyl 2-(4-ethoxyphenyl)
Arylpropyl ether insecticides such as -2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, other insecticides, acaricides, or fungicides It is also possible to create a multipurpose composition with even greater efficacy by mixing it with agents, nematicides, herbicides, plant growth regulators, fertilizers, BT agents, insect hormones, and other agricultural chemicals. You can also expect good results. 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 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 (butylated hydroxyanisole), phenol derivatives, such as
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
0.0001-95% by weight, preferably 0.001-50% by weight
Contain. When applying the compound of the present invention, the amount of active ingredient is generally 300g to 1g, preferably 100g to 2g, more preferably 20g per 10 ares.
~5g. [Example] Next, the method for producing an aromatic alkane compound of the present invention will be explained in more detail by giving synthesis examples below. Synthesis Example 1 Synthesis of 1-pentafluorophenyl-4-(4-ethoxyphenyl)-4-methylpentane (1) 10 ml of diethylene glycol dimethyl ether
diethyl pentafluorobenzylphosphonate
After adding 1.5 g of 3-(4-ethoxyphenyl)-3-methylbutyraldehyde and 1.0 g of potassium t-butoxide, 1.0 g of potassium t-butoxide was added and the mixture was stirred at 60°C for 2.0 hours. The reaction mixture was poured into water and extracted with benzene. After washing the extract with water and drying, the solvent was distilled off under reduced pressure. Column chromatography of the residue (silica gel, developing solvent: benzene)
1-pentafluorophenyl-4-
0.40 g of (4-ethoxyphenyl)-4-methyl-1-pentene was obtained. ν ^Neat _nax (cm ^-1 ): 1510, 1490, 1250, 1050, 980 (2) 20ml of ethyl acetate in a 200ml autoclave, 5
%Pd-C0.07g, 1-pentafluorophenyl-4-(4-ethoxyphenyl)-4-methyl-
0.35 g of 1-pentene was charged. 10 with hydrogen gas
The pressure was increased to Kg/cm ² G, and the mixture was stirred at 85° C. for 3.5 hours. The catalyst was filtered off and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: benzene-hexane (2:1)) to obtain 0.32 g of 1-pentafluorophenyl-4-(4-ethoxyphenyl)-4-methylpentane. n ²⁰ _D 1.5054 δ _CCl4TMS (ppm): 1.25 (s, 6H), 1.38 (t, J=6.
9Hz,
3H), 2.51 (t, J = 8.1Hz, 2H), 3.95 (q,
J = 6.9Hz, 2H), 6.67 (d, J _AB = 8.1Hz, 2H)
ABtype7.08 (d, J _AB =8.1Hz2H)ABtype Next, some formulation examples 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, Solpol 355S (a mixture of nonionic surfactant and anionic surfactant,
Toho Chemical (registered trade name) 10 parts and 70 parts of xylene are stirred and mixed to form 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 After adding 5 parts of a surfactant to 20 parts of the compound of the present invention and mixing well, 75 parts of diatomaceous earth is added and mixed with stirring in a Laikai machine to prepare a wettable powder. Formulation Example 4 2 parts of metha-tolyl N-methyl carbamate was added to 0.2 parts of the compound of the present invention, and 0.2 parts of PAP (isopropyl acid phosphate, registered trademark of Nihon Kagaku Kogyo, physical property improver) was added to each of the compounds, and dissolved in 10 parts of acetone. Add 97.6 parts of powder clay, stir and mix in a laikai vessel, and evaporate the acetone to form a powder. Formulation Example 5 To 0.2 parts of the compound of the present invention, 2 parts of Ofnatsu (registered product name of Mitsui Toatsu Chemical) was added, further 0.2 parts of PAP (as mentioned above) was added, dissolved in 10 parts of acetone, and 97.6 parts of powder clay was added. The mixture is stirred and mixed in a Raikai vessel, and the acetone is evaporated 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 (mixture of nonionic surfactant and anionic surfactant, trade name of Toho Chemical Co., Ltd.) to 0.5 parts of the compound of the present invention and 5 parts of Offnuc (described above), and add 89.5 parts of xylol. If it is dissolved in a portion, it becomes 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 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 (3:5: tab flour: lees flour: wood flour) was added.
After uniformly stirring and mixing 99.5 parts of (mixed at a ratio of 1:1) and evaporating the methanol, 150 ml of water was added and the mixture was thoroughly kneaded and molded and dried to produce 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 (carboxymethylcellulose, Daiichi Kogyo Seiyaku product name), 2 parts of Sunextract (ligninsulfonic acid-Na salt, Sanyo Kokusaku pulp product), add water and granulate to obtain the optimal granules. If the particles are sized to a specific diameter, they become granules. Next, in order to clarify that the compound of the present invention has excellent insecticidal and acaricidal effects and low toxicity to fish, test examples are shown below. In addition, the compounds (a) to (g) shown below were used as comparative compounds and prepared and tested in the same manner as the compounds of the present invention. All tests were conducted in duplicate, and the results are shown as the average value. (a) DDVP (b) Ophunac (c) Diazinon (d) Methomyl (e) Kelsen (f) PCP sodium salt (g) Fuenvalerate Pesticide Science Vol. 7 , 241 (1976) Test example 1 Effect on Spodoptera spp. Formulation example The emulsion of each test compound prepared in step 1 is diluted with water to a predetermined concentration, and sweet potato leaves are thoroughly immersed. After air-drying, the treated leaves were placed in plastic cups with a diameter of 10 cm, and 10 3rd instar larvae of Spodoptera were released at a time, and their survival was examined 48 hours later. The results are shown in Table 1. The test compounds are indicated by the above compound symbols (the same applies hereinafter).

[Table] Test Example 2 Effect on black leafhopper Four to five paddy rice seedlings at the three-leaf stage were tied together and sprayed with 3 ml of emulsion of each test compound prepared in the same manner as in Test Example 1. After air-drying, the seedlings were covered with a wire mesh cylinder, 10 female adult leafhoppers were released, and the number of dead insects was counted 48 hours later. The results are shown in Table 2.

[Table] Test Example 3 Effect on German cockroaches Add 1 ml of an acetone solution of each test compound at a specified concentration to a deep-type shear dish with a diameter of 9 cm and a height of 9 cm, and let stand to evaporate the acetone. To prevent insects from escaping,
Butter was applied to the upper part of the inner wall of the chamber, and 10 adult female cockroaches were released per chamber, and the number of dead insects was counted 48 hours later. The results are shown in Table 3.

[Table] Test Example 4 Effect on two-spotted spider mites Place a leaf disc (diameter 20 mm) of kidney bean leaves on absorbent cotton moistened with water, and inoculate 20 adult female two-spotted spider mites. After standing for a day and night, 3ml of a 200ppm emulsion of the test compound prepared in the same manner as Test Examples 1 and 2.
was sprayed using a spray tower with a diameter of 20 cm and a height of 60 cm, and the number of dead insects was counted 24 hours later. The results are shown in Table 4.

[Table] Test example 5 Toxicity to fish Fill a tank with width 60cm, height 30cm, and depth 40cm,
Ten old carp fish, each 5 cm in length, were released and allowed to acclimate.
Add an acetone solution of each test compound to 1/100 of the amount of water.
The concentration in the water was adjusted to 1.0.1 ppm, and the number of living and dead animals and the effects were investigated at each elapsed time.

[Table] [Effects of the Invention] The aromatic alkane compound represented by formula () according to the present invention is highly safe for warm-blooded animals and fish, and exhibits extremely high insecticidal and acaricidal activity. The aromatic alkane compound represented by the formula () according to the present invention is easily provided and is industrially extremely useful as an agricultural chemical.

Claims (1)

[Claims] 1 Formula () An aromatic alkane compound represented by 2 formula () An insecticide and acaricide characterized by containing an aromatic alkane compound represented by the following as an active ingredient.