JPS6321641B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the formula This is a repellent for harmful animals such as insects, mites, and molluscs, containing one or more of the following polyether antibiotic C-41 or its salts as an active ingredient. Antibiotic C-41 was published in Chemical Communications, 1971, regarding its production method and physical and chemical properties.
pp. 927-928, 1975, p. 533, and Journal of the American Chemical Society.
Society), 1951, Vol. 73, pp. 5295-5298, etc., as antibiotic X-206, and is already a known compound. However, nothing has been described about the effects of these compounds on harmful animals such as insects, mites, and molluscs. As a result of various studies on the use of antibiotic C-41, the present inventors unexpectedly found that antibiotic C-41 and its salt compounds are extremely effective in exterminating harmful animals such as insects, mites, and molluscs. They discovered something and completed the present invention. That is, the present invention is a pest control agent characterized by containing one or more of antibiotic C-41 or its salts as an active ingredient. Salts of antibiotic C-41 used in the present invention include, for example, sodium salts, potassium salts, ammonium salts, calcium salts, and magnesium salts, but are not limited to these and many other salts can be mentioned. Compounds combined with cationic substances are also included. Note that the desired compound as a free salt or various salts can be easily produced by operations such as a manufacturing process or a recovery process. Conventionally, DDT, BHC, parathion, Many insecticides such as Endrin and Deiltrin have been used in large quantities, but while these insecticides are extremely effective against pests, they are highly toxic and pose a great risk of poisoning to humans and livestock. , its use is currently prohibited in our country. In addition, organic phosphorus agents such as parathion, DDVP, Marathon, Kirvar, BHC,
Organic chlorine agents such as DDT, Kelsene, and chlorobenzilate, carbamate agents such as NAC, MTMC, and BPMC, and pyrethroid agents such as pyrethrin and allethrin have been used for pest control purposes. A frightening phenomenon is occurring in which some species develop resistance. In other words, there is currently an urgent need to develop agricultural chemicals that are highly selective between warm-blooded animals and pests, and are also effective against pests that are resistant to the drugs. As a result of research into the physiological activities of various antibiotics as described above, the present invention has revealed that antibiotic C-41 and its salts have strong insecticidal and acaricidal activities.
Furthermore, it has excellent activity against harmful animals such as insects, mites, and molluscs that are resistant to various drugs. The compound of the present invention causes almost no phytotoxicity to plants, has a precise effect, and can be used as a pesticide against a wide range of insects, such as sucking insects, biting insects, mites, and other plant parasitic pests. Alternatively, it can be applied to exterminate and exterminate husk pests, sanitary pests, etc. In other words, examples of Coleopteran insects include Sitophilus zeamais, Tribolium castaneum, and Epilachna.
vigintioctomaculata) Anomala rufocuprea Lepidopteran insects include Lymantria dispar, Pieris rapae, Prodenia litura, Chilo suppressalis, Malacosoma neustria, Adoxophyes orana, Ephestia cautella) Examples of hemiptera insects include Nephotettix cincticeps, Nilaparvata lugens, and Pseudococus.
comstoki) Green peach aphid (Myzus persicae) Apple aphid (Aphis pomi) Red radish aphid (Rhopalosiphum)
Pseudobrassicae) Examples of insects in the order of Mughoptera include the house fly (Musca domesticavicina), Aedes aegypti, Hylemia platura, Culex pipiens, Culex pipiens, Anopheles sinensis, and Culex triteniorhynchus. us) Two-spotted spider mite (Tetranychus ulticae) Citrus spider mite (Panonyehus citri) Citrus rust mite (Aculus pelekassi) Cyclamen dust mite (Tarsonemus)
pallidus) woolly mite (Tyrophagus dimidiatus), house dust mite (Ornithonyssus bacoti), etc. On the other hand, the development of exterminating agents for molluscs has become an urgent issue. In other words, terrestrial molluscs such as slugs and snails, which are great enemies of vegetables and flowers as well as sanitary pests, and freshwater molluscs such as shellfish, which serve as intermediate hosts for schistosomiasis and hepatic dystoma. The damage caused by these molluscs has become a worldwide problem. Currently, the chemicals used to exterminate these are copper sulfate, iron sulfate, slaked lime, PCP sodium salt, metaldehyde, etc. for land molluscs, and PCP sodium salt, metaldehyde for freshwater molluscs.
Pesticides containing 3,5-dibromo-4-oxy-4'-nitroazobenzene or heavy metals are used, but these drugs have weak control effects and
Because it is highly toxic to fish, it is not a drug that is satisfactory in terms of safety or environmental health. Therefore, it is desired to develop a more effective and highly safe pesticide. The compounds of the present invention exhibit fast-acting and powerful action against terrestrial and freshwater molluscs, and are fully satisfactory as pesticides. That is, examples of land molluscs include Euhadra quaesita, Fruticicola despecta, and Fruticicola despecta.
sieboldiana) Allopous clavulinum (Zonitoides arboreus)
kyotoensis) Stereophaedusa japonica) Slug (Incillaria confusa) Koura slug (Limax flavus). In addition, examples of freshwater molluscs include Bulimus striatulus rar.
Examples include Bulimus striatulus, Onchomelania nosophora, Biomphalaria glabrate, and Limnaea (Galba) ollura. When the compound of the present invention is used as a pest control agent for insects, mites and molluscs,
It can be used directly as it is after being diluted with water, or it can be used in various formulations by using adjuvants and methods commonly used in the agricultural chemical manufacturing field. Auxiliary agents here are inert solvents and carriers or fillers. Furthermore, various surfactants, organic raw materials, stabilizers, spreading agents (fixing agents), synergists, etc. can be used. Examples of the solvent include water, n-hexane, benzene, toluene, xylene, xylol, petroleum ether, chlorobenzene, methylene chloride,
Ethylene chloride, carbon tetrachloride, trichlorethylene, ethyl alcohol, methyl alcohol,
Examples include propyl alcohol, butyl alcohol, ethylene glycol, ethyl ether, ethylene oxide, dioxane, monochlorobenzene, acetone, ethyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, cyclohexanone, and cyclohexane. Examples of carriers or fillers include talc, clay, bentonite, diatomaceous earth, vermiculite, calcium carbonate, wood chips, synthetic alumina, white carbon, phenolic resin, urea resin, vinyl chloride resin, glucose, starch, dextrin, meat extract. , glycerin, molasses, starch syrup,
sucrose, glucose, fructose, yeast, bone meal,
Examples include fishmeal, crude oil, soybean flour, wheat germ, rice bran, and bran. Examples of surfactants include sodium laurate, alkylaryl sulfonate, sodium alkylnaphthalene sulfonate, laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, polyoxyethylene alkylaryl ether, polyoxyethylene alkyl phenyl Examples include ether, polyoxyethylene noniphenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan monolaurate. Examples of organic raw materials include sodium alginate, polyvinyl alcohol (PVA), soapless soap, casein lime, coumaron, indene resin, polyvinyl butyl ether, halogenated hydrocarbons (freon), dicyandiamide, nitrite, zinc powder, and perchloric acid. Spreading agents (sticking agents) such as salts, dichromates, and nitrocellulose; combustion agents used in aerosols and smokers; and phytotoxic substances such as zinc sulfate, ferrous chloride, copper nitrate, chlorophyll and chlorophyll derivatives. Examples include dispersion stabilizers and synergists such as reducing agents, casein, tragacanth, carboxymethyl cellulose (CMC), and polyvinyl alcohol (PVA). Typical formulations of the compounds of the present invention include:
Examples include emulsions, wettable powders, powders, granules, tablets, aqueous solutions, suspensions, solutions, smoking agents, aerosols, pastes, and the like. The active ingredient of the present invention in these above-mentioned preparations is 0.1 to 90% by weight, preferably
In actual use, the active ingredient content in the various formulations and spray preparations described above is generally between 0.0001 and 30% by weight.
Weight %, preferably in the range from 0.003 to 15 weight %, is suitable. Further, the content of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, place, time, and the occurrence of harmful animals such as insects, mites, and molluscs. The compound of the present invention may also be used, if necessary, with other agricultural chemicals such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant growth regulators, rodenticides,
It can also be used in combination with or mixed with attractants, fungicides, algae control agents, fertilizers, etc. The various formulations or spray preparations containing the active ingredients of the present invention can be applied by the application methods commonly used in the field of agrochemical manufacturing, such as spraying, dusting, dusting, water surface application, soil application, fuming, fumigation, etc. This can be done by surface application (e.g. dressing, coating, coating, wrapping), dipping, baiting, etc. It can also be used by a so-called high-concentration micro-spraying method. In this method it is possible to contain 90-100% by weight of active ingredient. When controlling pests using these methods, the amount of active compound applied per 10 ares is approximately 2 to 2.
2000gr is used, preferably 10-500gr. However, in special cases it may be possible, or even necessary, to exceed or fall below these ranges. An example of producing antibiotic C-41 of the present invention will be explained. Production example Glucose 3%, dry bouillon (Nissui Pharmaceutical)
1%, yeast extract 0.3%, calcium carbonate 0.3
Streptomyces sp. C-41 was inoculated into a medium supplemented with 5% and cultured with shaking at 28°C for 72 hours.
200ml of this culture solution was mixed with 2% glucose, 1% soluble starch, 1% soybean oil, 1% soybean flour, 0.025% dipotassium hydrogen phosphate, and 0.05% magnesium sulfate (7H ₂ O).
%, calcium carbonate (0.4%), inoculated into a 30-capacity jar fermenter containing 20% of medium supplemented with 28% calcium carbonate;
The culture was carried out with stirring at 10°C for 100 hours at an aeration rate of 10/min. This culture solution is separated into bacterial cells and liquid, and the bacterial cells are
20 in acetone, stirred for 2 hours, and filtered.
After concentrating under reduced pressure until the acetone is distilled off, the mixture is extracted with ethyl acetate. Adjust the pH of the liquid to 4 and 20
The mixture was extracted with ethyl acetate, and the ethyl acetate extracts were combined and dehydrated over anhydrous sodium sulfate. Next, the ethyl acetate extract was concentrated under reduced pressure until the ethyl acetate was distilled off, and the oily residue was dissolved in benzene and passed through a column packed with 500 ml of silica gel (Wako Gel C-200) to dissolve benzene, benzene:acetone (95: 5), benzene: acetone (90:
10), benzene:acetone (80:20) was eluted in this order, and the antibacterial active fraction was collected and the solvent was distilled off to obtain 13.5 g of crude antibiotic C-41. This crude material was dissolved in benzene and passed through a column packed with 200 ml of silica gel (Merck Silica Gel 60) to produce benzene, benzene:acetone (95:5), benzene:acetone (90:10), benzene:acetone (85:15). ) and benzeneacetone (80:20), and the antibacterial active fraction was collected and the solvent was distilled off, yielding 12.2 g of colorless needle-like crystals of antibiotic C-41. 3 g of the colorless needle crystals of antibiotic C-41 thus obtained are dissolved in 100 ml of ethyl acetate. Dissolve 5 g of soda carbonate in 100 ml of distilled water, add it to a separating funnel with ethyl acetate, shake, remove the aqueous layer, add 100 ml of distilled water, shake, remove the aqueous layer, and add acetic acid. The ethyl layer was concentrated under reduced pressure to remove ethyl acetate, yielding 2.6 g of colorless needle crystals of antibiotic C-41 sodium salt. When the colorless needle-like crystals of antibiotic C-41 sodium salt thus obtained are recrystallized from methanol, crystals that are efflorescent and devitrified are obtained, with a melting point of 193
~194℃. Literature value (APRaun [E. Lillya
Co.], USP 3937836), the melting point is 185-187°C. Recrystallization from acetone yields stable crystals with crystalline acetone. This substance is well soluble in organic solvents such as acetone, chloroform, and methanol, and is insoluble in water. Also, it does not absorb UV rays. C-13 NMR spectrum: Chemical shift δ value of CDCl ₃ (TMS standard) 182.7, 108.5, 99.0, 98.0, 88.8, 86.1, 82.5,
82.1, 80.6, 79.4, 73.2, 71.9, 70.3, 70.2,
68.7, 68.3, 50.2, 45.2, 43.3, 42.6, 41.4,
39.1, 38.8, 36.5, 34.62, 34.57, 34.3, 32.8,
32.5, 31.5, 31.2, 30.3, 28.9, 27.4, 27,
2, 27.0, 24.4, 20.3, 19.7, 17.9, 17.0,
16.7, 15.8, 15.5, 10.4, 10.3, 8.3. The molecular formula is C ₄₇ H ₈₁ O ₁₄ Na (molecular weight 893.14), and its elemental analysis values are: C H N Theoretical value (%) 63.21 9.14 0.0 Actual value (%) 63.05 9.16 0.0. It was determined by its chemical structure and X-ray diffraction method. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. The compound of the present invention refers to the free form or various salt compounds of antibiotic C-41, and can be applied to any formulation. Example 1 Compound of the present invention 20 parts by weight Diatomaceous earth 60 Karyon 15 Polyoxyethylene alkyl phenyl ether
5. Mix these components well, crush them, and use them as a wettable powder. Example 2 Compound of the present invention 40 parts by weight
10 parts by weight Mix these components thoroughly and use as an emulsion. Example 3 Compound of the present invention 5 parts by weight Talc 31 Clay 63 Sodium dotecylbenzenesulfonate
1. Mix these ingredients well, mix and crush and use as a powder. Example 4 Compound of the present invention 2 parts by weight Kesilon 78 Versicol AR-50 (manufactured by Versicol)
20 〃 Mix these ingredients thoroughly and use as an oil agent. Example 5 Compound of the present invention 10 parts by weight Bran 44 Wheat flour 40 Cane sugar 5 Sorbic acid 1 These ingredients were mixed, 30 parts by weight of water was added little by little, kneaded until homogeneous, and granulated. Granulate with a machine
Dry with warm air at 40-50℃ and use as granules. Next, it can be recognized from various test results that the compounds of the present invention exhibit excellent lethal effects against harmful animals such as insects, mites, and molluscs.
The effects of the present invention will be explained based on the test results by giving examples. Test Example 1 15 ml of a hydrating powder prepared in the same manner as in Example 1 diluted with water to a predetermined concentration was sprayed on the stems and leaves of three potted rice plants (plant height 10-15 cm), and the mixture was allowed to cool to room temperature. After air-drying, cover with a wire mesh with a diameter of 9 cm and a height of 20 cm, and place 20 to 30 carbamate-resistant black leafhopper adults in the mesh, place in a constant temperature room at 25 ° C, and count the number of dead insects after treatment. We investigated each progress. The results are shown in Table 1.

[Table] Test Example 2 Peach branches (10 to 15 cm) infested with the green peach aphid and the green peach aphid parasitic on a potted eggplant seedling with a diameter of 16 cm were hydroponically cultured in a 50 ml flask. Dilute the emulsion prepared in the same way to the specified concentration and spray 20ml each.
Place it in a temperature controlled room at 25℃ and measure the number of parasitism (dead insects) after spraying.
were investigated every number of days. The results are shown in Table 2.

[Table] Test Example 3 Put 200 ml of a diluted solution of the oil solution prepared in the same manner as in Example 4 to a specified concentration in a waist-high shear dish with a diameter of 9 cm, and add 25 ml of organic phosphorus agent-resistant Chicae 4th instar larvae to the solution. ~30 insects were placed in a constant temperature room at 25°C, and the number of dead insects was investigated as the number of days passed after treatment.
The results are shown in Table 3.

【table】

[Table] Test Example 4 Put 1 ml of a diluted oil solution prepared in the same manner as in Example 4 to a specified concentration in a waist-high shear dish with a diameter of 9 cm, place 30 old house fly larvae in this, and heat at 25°C. The number of dead insects was counted after 24 hours and the killing rate was calculated. The results are shown in Table 4.

[Table] Test Example 5 20 ml of a solution prepared by diluting the hydrating powder prepared in the same manner as in Example 1 to a predetermined concentration was uniformly sprayed on cabbage seedlings (four-leaf stage) planted in 12 cm diameter pots. After the chemical solution was air-dried at room temperature, it was covered with a glass cylinder with a diameter of 9 cm and a height of 20 cm (top surface covered with a glass cylinder).
The number (rate) of dead insects was investigated as the number of days after treatment was placed in a constant temperature room at ℃. The results are shown in Table 5.

[Table] Test example 6 Green beans grown in a pot with a diameter of 9 cm (cotyledon development stage)
The leaves were inoculated with 40 adult female insects of two-spot spider mites, which were chemically sensitive and resistant to organophosphates, and resistant to organophosphorus and organochlorine agents, at a rate of 40 per pot.
After a day, 20 ml of a solution prepared by diluting the hydrating powder prepared in the same manner as in Example 1 to each predetermined concentration was sprayed on each pot, and the pots were placed in a greenhouse to examine the number of parasitic larvae on the 10th day of treatment. The results are shown in Table 6. In addition, the number of insects in the control drug and untreated plots increased compared to the sample number due to continued egg laying.

[Table] Test Example 7 Cabbage seedlings (4-leaf stage) grown in pots with a diameter of 12 cm were uniformly sprayed with 20 ml of a solution prepared in the same manner as in Example 1, in which the hydrating powder was diluted to a predetermined concentration.
After air-drying at room temperature, a glass cylinder with a wire mesh on the top (diameter 9
cm, height 20 cm). Next, 10 to 20 slugs with a body length of 4 to 6 cm were placed in this, placed in a constant temperature room at 25℃, and the number of deaths (mortality rate) was investigated over the course of days after treatment. We also investigated. The degree of damage to cabbage leaves was determined using the following criteria. Damage Judgment Criteria: 0: No feeding damage was observed at all. 1: The surface of the leaf was slightly damaged. 2: The surface of the leaf was damaged by about half. 3: The leaf was severely damaged. It is shown in Table 7.

【table】

[Table] Test Example 8 A 200% solution of hydrating powders prepared in the same manner as in Example 1 diluted to each predetermined concentration was placed in a waist-high shear dish with a diameter of 9 cm.
ml, add Mametanishi (20~20 ml per pot)
25 individuals were placed in a constant temperature room at 25°C, and the number of deaths (mortality rate) was investigated as the number of days passed after treatment. The effect was judged by touching the antennae of a stationary shellfish with a thin wire, and if it did not move completely, it was judged as dead. The results are shown in Table 8.

【table】

[Table] Test Example 9 One solution prepared by diluting the emulsion prepared in the same manner as in Example 2 to each predetermined concentration was placed in a glass pot (5 water tanks) with a diameter of 20 cm, and Biomphalaria was added to the pot.
Place 20 to 25 adult Gravrate shellfish (body length 2 to 2.5 cm) per pot, cover the top with wire mesh, and place 25
The cells were placed in a constant temperature room at ℃, and the number of deaths (mortality rate) was investigated as the number of days passed after treatment. In order to judge the effect, a shellfish that was stationary at the bottom of the pot was placed in water without the drug, and if no change (movement) occurred after 2 hours, it was judged as dead. The results are shown in Table 9.

【table】

【table】

Claims (1)

[Claims] 1 formula A pest control agent characterized by containing one or more of the following antibiotic C-41 or its salts as an active ingredient.