KR20170101691A - A insecticidal composition comprising an amide - Google Patents

Abstract

The present invention relates to an insecticidal composition comprising a compound represented by chemical formula 1 or 2, or agrochemically acceptable salt thereof; and to a manufacturing method of the compound. Since the compound exhibits an excellent insecticidal effect against larvae of the cabbage moth, the compound can be usefully used as an environmentally friendly insecticide in the control of pests harmful to animals and plants.

Description

A insecticidal composition comprising an amide < RTI ID = 0.0 >

The present invention relates to an insecticidal composition comprising amide, a composition for insecticidal use comprising a mushroom extract containing amide or a fraction thereof, and a method for insecticidal use using said composition.

In modern agriculture, pesticides are indispensable for the stable mass production of high quality crops. These pesticides vary in their use depending on the type of crops and target pests, and therefore hundreds of pesticides are manufactured and sold in the country. However, due to the abuse and abuse of highly toxic pesticides over decades, many adverse effects such as the emergence of insect pests or the appearance of resistant pests, toxic manifestations against human insects, and environmental pollution have appeared.

The pesticides used for the protection of crops should be effective against weeds and pests, but they should not be toxic or not toxic to humans, plants and animals, and should not easily decompose in the environment and act as environmental pollutants. In order to solve various problems, researches on low toxicity, non-toxic, or non-pollution biological pesticides are actively conducted.

Biological pesticides include microbial pesticides, biochemical pesticides, and natural pesticides. The microbial pesticide refers to an agricultural microbial control agent using living microorganisms such as fungi, bacteria, viruses and protozoans, and the biochemical pesticide refers to an active substance or an herbal medicine controlling agent for extracting and using natural compounds produced in the natural environment or related to signal transduction. The biochemical pesticide refers to natural pesticides composed of natural ingredients such as animals and plants, pheromones, enzymes and minerals, and pesticides produced in plants by genes introduced into plants. Such bio-pesticides are not persistent and do not affect human beings, livestock and the environment and can be used as a substitute for chemical synthetic pesticides. However, environmentally friendly pesticides are generally not easy to handle raw materials, and their control agents are very low compared to chemical pesticides. In addition, most bio-pesticides and natural pesticides are not economically effective and effective because they are expensive, and their effectiveness is very limited, their effectiveness is not very effective, .

However, due to excessive use of chemical synthetic pesticides, pollution of soil and water quality, environmental problems such as ecosystem disturbance due to soil microorganisms and natural enemy reduction are becoming big social issues. In recent years, the continuous and continuous use of pesticides has caused a problem of resistance to poor control effect even when a large amount of pesticide is sprayed, and even when a pesticide which is often highly toxic in agricultural products is detected as an excessive value, . In addition, various undesirable direct and indirect side effects have been caused by this, and pesticide residues in crops have been a fatal cause for the human body to ingest.

For this reason, a variety of researches have been conducted on the development of pesticides which are environmentally friendly and harmless to human beings, easy to handle, low in production cost and high in control, and to reduce the amount of pesticide used. As a conventional known technique for pesticidal compositions, Korean Patent Registration No. 10-0415107 discloses a method for producing ginkgo leaf, a method for producing the ginkgo leaf, a method for producing the ginkgo leaf, a method for producing a pesticide for an antifungal agent in Korean Patent No. 10-0338712, -0285208, a natural soil treatment and insecticide composition in U.S. Patent No. 6051233, a pest control using surfactant and terpene in USP 6582712, a disinfectant in USP 6548085 Compositions and the like have been disclosed, but a satisfactory result can not be obtained from them.

Under these circumstances, the present inventors have made intensive efforts to search for an active substance exhibiting an environmentally friendly and low toxic insecticidal activity from the extracts of plants widely present in the natural world. As a result, it has been found that the mushroom extract and the amide compound isolated from the extract have excellent insecticidal effect The present invention has been completed.

An object of the present invention is to provide an insecticidal composition comprising a compound represented by the following general formula (1) or (2) or a salt thereof as an active ingredient.

[Chemical Formula 1]

(2)

Another object of the present invention is to provide an insecticidal composition comprising, as an active ingredient, an alcoholic extract having a carbon number of 1 to 4, or a fraction thereof, of the compound of the above formula 1 or 2, or a salt thereof will be.

It is another object of the present invention to provide a method for insecticidal use using the composition.

According to one aspect of the present invention, there is provided an insecticidal composition comprising a compound represented by the following general formula (1) or (2), or a salt thereof as an active ingredient.

[Chemical Formula 1]

(2)

The compound of formula (1) or (2), which is an amide compound isolated from the mushroom extract, has a very excellent insecticidal effect, and the composition containing the compound or its salt is environmentally friendly and has low toxicity to humans, plants and animals It can be very useful as a composition. In the present invention, it was first confirmed that the compound represented by Formula 1 or 2 has an insecticidal effect. In addition, the compound represented by the above formula (1) or (2) can be effectively used to control pests or larvae of the insecticide resistant to the insecticide.

The compound represented by Formula 1 is referred to as piperrolein B, and the compound represented by Formula 2 is referred to as piperchabamide D.

In the present invention, the compound represented by Formula 1 or 2 can be isolated from natural materials by known methods or synthesized by a known chemical synthesis method. The compounds represented by the above formula (1) or (2) may be commercially available. Specifically, the compound represented by Formula 1 or 2 may be isolated from fenugreek, but is not limited thereto.

In one embodiment of the present invention, n-hexane, chloroform, ethyl acetate and water fractions were prepared from the methanol extracts of Hojok. The chloroform fractions having the highest insecticidal effect were subjected to silica gel column chromatography, reversed phase chromatography, Compounds 1 and 2 were separated using liquid chromatography and identified. As a result, the respective amide compounds, piperoraine and piperazabimide, were identified (Examples 1 and 2).

In addition, in one example of the present invention, it was confirmed that Compounds 1 and 2 have excellent insecticidal effect against Larval Larval Larvae (Table 1).

In addition, in one embodiment of the present invention, it was confirmed that Compound 2 has excellent insecticidal effect against cotton budworm larvae (Table 2).

In the present invention, the salt of the compound represented by the general formula (1) or (2) is generally used in the art, and there is no limitation as long as the salt has an insecticidal effect. Specifically, the inorganic base includes alkali metal, Alkaline earth metals such as calcium and magnesium and ammonia and the like. The organic base may be pyridine, collidine, triethylamine and triethanolamine. The organic acid may be formic acid, acetic acid, tartaric acid, malic acid, citric acid, oxalic acid, , Methanesulfonic acid, and p-toluenesulfonic acid.

When the compound of the present invention is used as an active ingredient of an insecticidal composition, it can be used as such or in the form of a salt without the addition of any other ingredients. The compound of the present invention may be mixed with a solid carrier, a liquid carrier, a gas carrier, or a transfer agent, or may be absorbed into a basic substance such as a porous ceramic plate or a nonwoven fabric and then added with a surfactant and, Can be formulated with pharmaceutically acceptable excipients such as oil sprays, emulsifiable concentrates, wettable powders, milk, granules, dust, aerosols, fumigants, vaporizable formulations, smoking formulations, toxic handouts, . Each of the above formulations usually contains from 0.01 to 99% by weight of one or more of the present compounds as an active ingredient.

Solid carriers that may be used in the formulation include fine powders or granules of clay materials such as kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, clay and clay; Various talc, ceramics and other inorganic materials such as sericite, quartz, sulfur, activated carbon, calcium carbonate and hydrated silica; And chemical fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride.

Liquid carriers include water; Alcohols such as methanol and ethanol; Ketones, such as acetone and methyl ethyl ketone; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and methylnaphthalene; Aliphatic hydrocarbons such as hexane, cyclohexane, kerosene and light oil; Esters such as ethyl acetate and butyl acetate; Nitriles, such as acetonitrile and isobutyrnitrile; Ethers such as diisopropyl ether and dioxane; Acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Halogenated hydrocarbons such as dichloromethane, trichloroethane and carbon tetrachloride; Dimethyl sulfoxide; And vegetable oils such as soybean oil and cottonseed oil.

The gas carrier or propellant may include Freon gas, butane gas, LPG, dimethyl ether, and carbon dioxide.

Base materials for use in toxic handouts include, but are not limited to, handles materials, such as grain powders, vegetable oils, sugars and crystalline cellulose; Antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid; Preservatives such as dehydroacetic acid; Non-food-preventing substances such as pepper powder; And an attractiveness flavor, such as cheese flavor and onion flavor.

Surfactants may include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylene derivatives thereof, polyethylene glycol ethers, polyhydric alcohol esters and sugar alcohol derivatives.

Adjuvants such as adhesives or dispersing agents include casein, gelatin; Polysaccharides such as starch, gum arabic, cellulose derivatives and alginic acid; Lignin derivatives, bentonites, sugars and synthetic water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acid.

Stabilizers include PAT (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert- 4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids and esters thereof.

The composition of the present invention may have an insecticidal effect against harmful nematodes, insects and larvae thereof. Specifically, the nematode may be selected from the group consisting of a cucumber root nematode, a rice nematode, and a rice root nematode. The pest is selected from the group consisting of a Chinese cabbage moth, a cotton moth, a tobacco moth, But is not limited thereto.

When the composition of the present invention is used as an agricultural insecticide or as a nematicide, the application amount of the compound represented by the general formula (1) or (2), or a salt thereof is usually 0.1 to 100 g per 10 acres. For emulsifiable concentrates, wettable powders, animal and other similar formulations used after dilution with water, the application concentration is usually in the range of 1 to 1,000,000 ppm. Application of granules, dust or other similar formulations is carried out as an undiluted formulation.

When the composition of the present invention is used as an insecticidal agent for preventing epidemics, or as a nematicide, an emulsifiable concentrate, a wettable powder, a milk animal, or other similar formulation, the compound represented by the formula (1) To be diluted to a concentration of 0.1 to 5,000 ppm, or may be applied directly to oil sprays, aerosols, fumigants, toxic handouts, anti-ticks or other similar formulations.

When the composition of the present invention is used as a live insect for the control of livestock such as cattle and pigs or for the control of parasites such as cats and dogs, known veterinary methods, such as tablets for capsules, , Bolus, food incorporation, suppository or injection; Or by injection of an oily or aqueous solution, by an injection process, or by using molded articles of suitable shape, such as collar and ear tags, for non-systematic control. In this case, the compound represented by the formula (1) or (2) or a salt thereof may be usually used in an amount of 0.001 to 1,000 mg per kg of the host body.

The application amount and concentration of the composition of the present invention may vary depending on the form of the formulation, application time, place and method, type of pest, degree of damage, and other factors.

The compositions of the present invention may be used in combination with other insecticides, nematicides, fungicides, fungicides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners and / or animal feeds, .

Another aspect of the present invention is to provide an insecticidal composition comprising an alcoholic extract having a carbon number of 1 to 4 or a fraction thereof as an active ingredient, which comprises the compound of the above formula (1) or (2) to provide.

The herbal extracts of the present invention or fractions thereof contain the compounds of the formulas (1) and (2) which have excellent insecticidal effect and can be used as an effective ingredient in insecticidal compositions.

In the present invention, the term " Piperis Nigri Fructus "refers to the fruit of pepper tree, which is also called pepper, oxycodone, orchard and marigold, and has been used as a spice.

The term "extract" of the present invention includes the extract obtained by the extraction treatment of the above-mentioned juice, the diluted or concentrated liquid of the extracted liquid, the dried material obtained by drying the extracted liquid, the adjusted product or the purified product of the extracted liquid, And extracts of all formulations which can be formed using extracts.

The extract can be extracted from a natural, hybrid, or variant plant of the plant, and can also be extracted from a plant tissue culture.

The method for producing the above extract is not particularly limited, and can be extracted according to a method commonly used in the art. Non-limiting examples of the extraction method include hydrothermal extraction, ultrasonic extraction, filtration, and reflux extraction. These may be performed alone or in combination with two or more methods. Further, in order to obtain a high-purity extract, the extract may be further extracted one or more times by the same method.

The type of the extraction solvent used for the preparation of the extract is not particularly limited, and any solvent known in the art can be used as long as an extract having the objective effect of the present invention can be obtained. For example, at least one solvent selected from the group consisting of water, an alcohol having 1 to 4 carbon atoms, ethyl acetate, acetone or chloroform may be used. More specifically, an alcohol having 1 to 4 carbon atoms can be used as a solvent.

In the present invention, the "alcohol extract having 1 to 4 carbon atoms" includes not only extracts of alcohol with 1 to 4 carbon atoms, but also extracts with alcohol having 1 to 4 carbon atoms and water.

In one embodiment of the present invention, the methanol extract of Hochos was prepared by adding 3 times methanol (relative to the dried hosiery weight) to 5 kg of hosomal and left at room temperature for 7 days.

The term "fraction " of the present invention means a product obtained by performing fractionation to separate a specific component or a specific component group from a mixture containing various various components.

The fractionation method for obtaining the fraction is not particularly limited and may be carried out according to a method conventionally used in the art, so long as the fraction having the objective effect of the present invention can be obtained. As a non-limiting example of the above-mentioned fractionation method, there can be mentioned a method in which a fractionated product is obtained by treating a pomegranate extract obtained by adding a solvent to a mulberry leaf to a predetermined fraction solvent.

The kind of the fraction solvent is not particularly limited, and any solvent known in the art can be used as long as the fraction having the objective effect of the present invention can be obtained. Non-limiting examples of the fraction solvent include water, alcohol, ethyl acetate, acetone, or an organic solvent such as chloroform. These may be used alone or in combination of two or more. Specifically, the fraction solvent may be selected from the group consisting of water, hexane, chloroform, ethyl acetate, and a mixed solvent thereof, but is not limited thereto.

In one embodiment of the present invention, n-hexane, chloroform, ethyl acetate and water fractions were prepared from the methanol extracts of Hojok, and the insecticidal effects of the respective fractions on the larvae were examined. As a result, , 5 in the ethyl acetate fraction and 1 in the water fraction, indicating that the chloroform fraction had the best insecticidal activity (Example 1).

Another aspect of the present invention provides a method for insecticidal use using the insecticidal composition.

The insecticidal composition of the present invention is not only excellent insecticidal effect but also is useful for insect pests and nematodes since it is derived from plants and is environmentally friendly and has extremely low toxicity to humans or animals.

The pests and nematodes are as described above.

Specifically, the insecticidal composition of the present invention can be sprayed over rice fields, fields, orchards, non-cultivated wastes, houses and the like using known methods, so that pests and nematodes are contacted with the composition of the present invention, So that insects and nematodes can be eliminated.

In addition, the method of the present invention can disperse the insecticide composition using the same method as the general pesticide scattering method. The time for dispensing the composition of the present invention may be pre-planting in the case of seed, seed potato or bulb; In the case of soil treatment, it may be at any time during the growth period after the actual planting, and may be planting, seedling or actual planting for improved efficacy; In the case of spreading or spreading foliage, it may be, but is not limited to, during the growing and growing period on the farm.

In addition, the method of the present invention can be used for the aforementioned insecticidal composition in combination with an intrinsic microbial agent, natural enemies (for example, natural enemies such as parasitic bee and carnivorous beetle, carnivorous mite, parasitic nematode, , Combinations with genetically modified crops, combinations with insecticides and insect repellents, but are not limited thereto.

In addition, the method of the present invention is characterized in that the insecticidal composition is applied to pests, nematodes or habitats thereof in an amount of 0.1 to 1000 μl / ml, more specifically 0.5 to 500 μl / Ml, 1 to 500 μl / ml, or 1 to 100 μl / ml, more specifically 5 to 500 μl / ml or 10 to 100 μl / ml.

In one embodiment of the present invention, Compound 1 or 2 was treated with a concentration of 1, 10 or 100 μg / ml in a cabbage moth larva, and it was confirmed that the insecticidal effect persisted for 4 days in a concentration-dependent manner (Table 1 and FIG. 7).

In addition, in Example 1 of the present invention, Compound 2 was treated with cotton budworm Moth moth larva at a concentration of 1, 10, or 100 μg / ml, and it was confirmed that the insecticidal effect persisted for 4 days in a concentration-dependent manner (Table 2) .

Since the amide compound of the present invention isolated from the mushroom extract has a very excellent insecticidal effect, the compound or its salt-containing composition is environmentally friendly and very useful as an insecticidal composition exhibiting low toxicity to humans, plants and animals .

Fig. 1 is a mass spectrometry spectrum of the insecticidal active compound 1 isolated from mulberry.
2 is a hydrogen nuclear magnetic resonance spectrum of the insecticidal compound 1 isolated from mulberry.
Fig. 3 is a carbon nuclear magnetic resonance spectrum of the insecticidal compound 1 isolated from mulberry.
Fig. 4 is a mass spectrometry spectrum of the insecticidal compound 2 separated from the hosoides. Fig.
Fig. 5 is a hydrogen nuclear magnetic resonance spectrum of insect-active compound 2 isolated from hosoides.
Fig. 6 is a carbon nuclear magnetic resonance spectrum of the insecticidal compound 2 separated from the mulberry.
Fig. 7 is a graph showing the insecticidal rate of the larvae of the cabbage moth larvae for 4 days by the insecticidal active compounds 1 and 2 isolated from the mosquito.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

Example  1: Isolation of compounds 1 and 2 having insecticidal activity

The Piperis Nigri Fructus used in this example was purchased from the herbal medicine building near the Daejeon Station of Daejeon Metropolitan City. The purchased horsetail was cleaned and dried in the shade, and then pulverized using a pulverizer. To 5 kg of the powdered hosiery, 3-fold methanol (relative to the dried hoso weight) was added, and the mixture was allowed to stand at room temperature for 7 days to extract and filtrate. The filtrate was concentrated under reduced pressure to obtain crude extract. In order to separate and purify the active substance from the crude extract, each fraction was separated using n-hexane, chloroform, ethyl acetate and water.

In order to search for fractions having high insecticidal activity among fractions using hexane, chloroform, ethyl acetate and water, a part of each of the above fractions was dried to prepare samples at a concentration of 1 mg / ml, 10 were treated for 1 day to determine insecticidal activity. As a result, two larvae in the normal hexane fraction, six in the chloroform fraction, five in the ethyl acetate fraction and one in the water fraction died, indicating that the chloroform fraction had the best insecticidal activity.

Thus, the chloroform extract layer was concentrated under reduced pressure to obtain 157.7 g. A step gradient solvent system consisting of n-hexane: ethyl acetate = 50: 1 to 100: 1 was used to separate the active substance. ≪ / RTI > column chromatography.

The insecticidal activity of the fractions having the highest insecticidal activity was measured in the fractions separated by the above method, and the fractions having the highest insecticidal activity among them were collected and applied to the reversed phase chromatography. The active fractions were separated by octadecyl group binding silica (ODS) gel using 50%, 60%, 70%, 80%, 90% and 100% methanol for the reversed phase chromatography.

The insecticidal activity of the fraction isolated by the above method was measured, and the 4th and 5th fractions, which were the most highly insecticidal fractions, were collected and concentrated under reduced pressure. In order to separate foreign matters mixed with the active substance, 75% and 80% % Methanol at 6 ml / min and 8 ml / min, respectively. Among them, the fractions having a high insecticidal activity were analyzed by high performance liquid chromatography (HPLC, YMC Jsphere ODS H-80) using 75% and 80% methanol at flow rates of 4 ml / min, 6 ml / min and 4 ml / (250 x 20 minutes)) to obtain each pure compound. The active substance was detected at UV 254 nm and 210 nm. The eluted peak at 31 minutes was collected and dried to obtain 36 mg of Compound 1, and the eluted peak was collected at 43 minutes and then dried to obtain 27 mg of Compound 2.

Example  2: Identification of compounds 1 and 2

Example  2-1: Analysis method

Fast atom bombardment mass spectrometry (FAB-MS) and nuclear magnetic resonance (NMR) analyzes were performed to analyze the molecular weight, molecular formula and mass of the active compound isolated in Example 1 above.

Example  2-2: Compound 1

As a result of the analysis of Example 2-1, the molecular formula of Compound 1 was C ₂₁ H ₂₉ NO ₃ via FAB-MS, and the molecular weight was measured as [M + Na] ⁺ m / z 343 (FIG. The ultraviolet absorbance of the compound was measured. As a result, the maximum absorption value was found at 260 nm, and it was estimated that dienamide was present in the structure of the compound. One methylene dioxyproton (δ 5.92, s) was observed from the ¹ H-NMR spectrum through nuclear magnetic resonance (NMR) analysis for the structural identification of the active compound 1, and 6.0 to 7.0 Five olefin prions were observed. On the other hand, methylene protons bound to -N- at δ3.54 and δ3.38 were observed, and 14 methylene protons could be observed between two methylene protons at δ2.30 and δ2.15 and between δ1.31 and 1.67 (Figs. 2 and 3). Detailed analysis of hydrogen ( ¹ H-) and carbon ( ¹³ C-) NMR spectra of Compound 1 is as follows.

Hydrogen nuclear magnetic resonance spectrum ^{(1 H-NMR) [300MHz} , chloroform _{-d 3, δ (ppm)]} : 6.88 (1H, br s, H-2 '), 6.74 (1H, m, H-5'), 6.73 (1H, br s, H -6 '), 6.27 (1H, d, J = 15.3 Hz, H-9), 6.03 (1H, dt, J = 15.9, 6.9 Hz, H-8), 5.92 (2H , s, H-7 ') , 5.75 (1H, d, J = 15.3 Hz, H-2), 3.54 (2H, t, J = 5.4 Hz, H-1 "), 3.38 (2H, t, J = 5.5 Hz, H-5 ") , 2.30 (2H, t, J = 7.5 Hz, H-2), 2.16 (2H, q, J = 6.6 Hz, H-7), 1.61 (4H, m, H-2 (4H, m, H-3 and 5), 1.45 (2H, m, H-6)

Carbon nuclear magnetic resonance spectra ^{(13 C-NMR) [75MHz} , chloroform _{-d 3, δ (ppm)]} : 24.57 (t, C-3 "), 25.37 (t, C-4"), 25.56 (t, C (T, C-2), 28.95 (t, C-5), 29.24 (t, C-6), 29.34 (t, C-2), 42.54 (t, C-1 "), 46.67 (t, C-5"), 100.85 (d, C-5 '), 120.14 (d, C-6'), 129.27 C-3 '), 147.87 (s, C-4'), 171.37 (s, C-

From the results of molecular weight measurements and NMR data, the compound 1 was found to be a colorless oily phase, and the active compound was a compound having the structure represented by the following formula (1), and the piperolein B containing piperidene (Kiuchi, F., Nakamura, N., Tusda, Y., Kondo, K. and Yoshimura, H. 1988. Studies on crude drugs effective on visceral larva migrans IV. identification of larvicidal priciples in pepper: Chem Pharm Bull 36 (7), 2452-2465). As a result, it was confirmed that the compound of the following formula (1) corresponds to the piperrolane ratio.

[Chemical Formula 1]

Example  2-3: Compound 2

As a result of the analysis of Example 2-1, the molecular formula of Compound 2 was C ₂₂ H ₃₁ NO ₃ via FAB-MS and the molecular weight was measured as [M + Na] ⁺ m / z 380 (FIG. In addition, as a result of measurement of ultraviolet absorbance of Compound 2, the maximum absorbed value was found at 260 nm, and absorption of shoulder was observed at 295 nm to 305 nm, so that the presence of conjugated dienamide in the structure of the compound was estimated. In addition, one methylenedioxyproton (5.93, s) was observed from the ¹ H-NMR spectrum through nuclear magnetic resonance (NMR) analysis for the structural identification of the active compound 2, Seven olefinic protons were observed between 7 and 7.3. Also, four methylene protons were observed between? 1.30 and 1.50 (FIGS. 5 and 6). Detailed analysis of hydrogen ( ¹ H-) and carbon ( ¹³ C-) NMR spectra of Compound 2 is as follows.

Hydrogen nuclear magnetic resonance spectrum ^{(1 H-NMR) [300MHz} , chloroform _{-d 3, δ (ppm)]} : 6.89 (1H, br s, H-2 '), 6.83 (1H, dt, J = 15.3, 7.5 Hz , 6.75 (1H, brs, H-6 '), 6.27 (1H, d, J = 15.9 Hz, H-11), 6.03 (d, J = 15.3, 7.5 Hz, H-10), 5.93 (2H, s, H-7 '), 5.75 (1H, d, J = 15.3 Hz, H- , 3.14 (2H, t, J = 6 Hz, H-1 "), 2.17 (4H, m, H-4 and H-9), 1.80 , H-5 and H-8), 1.33 (4H, m, H-6 and H-7), 0.93 and 0.91

Carbon nuclear magnetic resonance spectra ^{(13 C-NMR) [75MHz} , chloroform _{-d 3, δ (ppm)]} : 20.11 (q, C-3 "and 4"), 28.19 (t, C-5), 28.59 (d (T, C-8), 31.97 (t, C-4), 32.84 (t, C-6), 29.92 ), 46.81 (t, C-1 "), 100.89 (t, C-7 '), 105.37 ), 123.60 (d, C-2), 129.32 (d, C-10 and C-11), 132.45 '), 147.91 (s, C-3'), 166.06 (s, C-1).

The compound 2 is a colorless crystalline powder, and from the results of molecular weight measurements and NMR data, the active compound has a structure of the following formula (2), which has an isobutyl group and has an amide bond (Morikawa, T., Matsuda, H., Yamaguchi, I., Pongpiriyadacha, Y. and Yishikawa, M. 2004. New), which is very similar to the structure of piperchabamide D contained in the structure amides and gastroprotective constituents from the fruit of Piper chaba : Planta Med. 70, 152-159). As a result, it was confirmed that the compound of the following formula (2) was in agreement with piperacibamid.

(2)

Example  3: Cabbage moth ( Plutella xylostella  L.) Insecticidal activity against larvae  Confirm

The test insect used in the present invention, Plutella The larvae of xylostella L. were distributed from the Insect Resource Center of Korea Research Institute of Bioscience and Biotechnology, Eun - dong, Yuseong - gu, Daejeon, Korea. Compounds 1 and 2 having insecticidal activity of the present invention were precisely weighed using an electronic balance, and the concentration to be used in the experiment was calculated in advance. The resulting solution was dissolved in acetone and mixed with 9 times of aqueous solution of 100 ppm of triton X-100. A solution of the insecticidal compound was prepared which was sequentially diluted and treated with the Chinese cabbage larvae.

The cabbage leaves of the moth larvae used in the experiment were grown in a uniform growth state without treating the insecticides. The leaves were discarded with a disc (diameter 3.0 cm), immersed in a prepared insecticidal compound for 30 seconds, Lt; / RTI > for 60 minutes. The control test was prepared in the same condition as the insecticidal test. In the insecticidal test, leaves treated with the active compound were placed on Petri dish (55 × 20 mm) with filter paper impregnated with distilled water, and the larvae of the second instar larvae of cabbage moths were transferred with a soft brush so that the larvae were not damaged. , Respectively. Then, the insecticidal compound-treated cabbage larvae were slaughtered at 24, 48, 72, and 96 hours while growing in a greenhouse (25 ± 1 ° C., 40 to 45% relative humidity, 16 L: 8 D) .

The control was treated in the same manner as in the above Compounds 1 and 2, except that 10% acetone solution instead of insecticidal active compound was treated with a mixture of 9 times 100 ppm aqueous solution of triton X-100.

The experiment was repeated three times and the half-life lethal concentration (LC ₅₀ ) was calculated according to the probit method of Finney (1982). Compound 1 or 2 at a concentration of 1, 10, and 100 μg / ml was treated with 1 ml each in a moth, and the degree of insecticidal activity was measured at intervals of 24 hours for 4 days. The results are shown in Table 1 and FIG.

As a result, it was confirmed that the insecticidal effect of the larvae of the Chinese cabbage larvae was increased over time in the group treated with Compound 1 or 2 as compared with the control without the compound treatment (Table 1). In addition, Compound 1 or 2 showed excellent insecticidal effect in a concentration dependent manner. In case of Compound 1, the insecticidal rate was 44.8%, 72.4%, and 79.2% after 4 days from 1, 10 or 100 μg / , And that of Compound 2 was 53.1%, 62.2%, and 96.7% after 4 days of treatment at the concentration of 1, 10, or 100 μg / ml, respectively.

Example  4: Cotton Goch moth ( Palpita indica ) Insecticidal activity against larvae  Confirm

Palpita indica was grown in an acrylic cage (30 × 30 × 30 cm) while cucumber seedlings and cucumber were supplied indoors. Indoor rearing conditions were 25-28 ℃, 16L: 8D, RH 50-60%, and salting activity was confirmed under the same conditions as the rearing condition.

  Compound 2 was diluted to various concentrations and the cucumber slice (5 × 2 cm) was immersed in the solution for 60 seconds. The filter paper (9 cm × 5 cm) was placed on a single petri dish (9 × 5 cm) and shade was placed on the shade. Ten larvae of the 3rd instar larvae were examined for insecticidal activity after 1, 2, 3, and 4 days of chemical treatment, and the experiment was repeated three times.

As a result, it was confirmed that, in the group treated with Compound 2, the insecticidal number of cotton budworm larvae increased with time, as compared with the control without treatment of the compound (Table 2). In addition, it was confirmed that the compound 2 exhibited excellent insecticidal effect in a concentration-dependent manner.

From the above results, it has been found that the compound represented by the general formula (1) or (2) or the salt thereof has a remarkably excellent continuous insecticidal effect in a concentration-dependent manner.

From the above description, it will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. In this regard, it should be understood that the above-described embodiments and experiments are illustrative in all aspects and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention without departing from the scope of the present invention as defined by the appended claims.

Claims (8)

An insecticidal composition comprising a compound represented by the following formula (1) or (2) or a salt thereof as an active ingredient:
[Chemical Formula 1]

(2)

.
The insecticidal composition of claim 1, wherein said compound is isolated from a fungus.
The insecticidal composition according to claim 1, wherein the composition has an insecticidal effect against at least one pest or a larva thereof selected from the group consisting of Cabbage moth, Cottonwood moth, Tobacco moth, and White moth.
The insecticidal composition according to claim 1, wherein the composition has an insecticidal effect against at least one nematode selected from the group consisting of cucumber root nymphs, rice nematodes and rice root nematodes.
An insecticidal composition comprising, as an active ingredient, an alcoholic extract having a carbon number of 1 to 4, or a fraction thereof, of the formula (1) or (2)
[Chemical Formula 1]

(2)

.
[Claim 6] The method according to claim 5, wherein the fraction is obtained by fractionating an alcoholic extract having 1-4 carbon atoms of Hojose with a solvent selected from the group consisting of water, hexane, chloroform, ethyl acetate and a mixed solvent thereof. Composition.
A method for insect pest or nematode using the composition of any one of claims 1 to 6.
The insecticidal method according to claim 7, wherein the compound represented by the following formula 1 or 2, or a salt thereof, is treated to an insect, a nematode or its habitat at a concentration of 0.1 to 1000 μl / ml:
[Chemical Formula 1]

(2)

.

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