JP5482993B2 - Spotted rice stink bug repellent - Google Patents

Description

  The present invention relates to a stink bug repellent and a repellent method, and a method for producing a stink bug repellent compound.

  In recent years, damage to crops by stink bugs has increased rapidly. In particular, spotted rice stink bugs dissolve the starch of rice seeds with digestive juice and absorb it. At this time, the sucked portion is easy for bacteria to propagate, and the area around the sucked trace is drastically changed to spotted rice. If speckled rice is mixed with harvested rice, the appearance and texture will deteriorate and the product value of the rice will decrease. For this reason, spotted rice stink bugs are regarded as important pests in rice cultivation. The cause of the frequent occurrence of stink bugs in recent years is that the area of fallow fields that have not been weeded has increased. This makes it easier for spotted rice stink bugs to breed even before the rice heads, and it is thought that the number of flying rice to paddy fields has increased.

  Measures against damage to stink bugs, especially spotted rice stink bugs, include spraying insecticides and cutting weeds on the shore. These measures must be taken frequently in order to control stink bugs that fly one after another. As a countermeasure against stink bugs, there is a method of spraying pesticides containing insecticides. As insecticides, MEP (fenitrothion), an organic phosphorus agent, PAP (fentoate), or a synthetic pyrethroid agent such as etofenprox, silafluophene, or a neonicotinoid compound is generally effective (non-patent literature). 1 etc.). However, there is a concern that the spraying of pesticides containing insecticides will affect the human body and ecosystem. Similarly, herbicide spraying has the potential to affect the human body and ecosystem. In recent years, the need for reduced pesticide farming has been called out. Also, weeding away weeds is important because it means that stink bugs overwinter and reduce the breeding place, but weeding work is a heavy labor and there is a risk of driving stink bugs in the field if the weeding time is wrong.

  Under such circumstances, it has been desired to develop an insecticide, herbicide, a new bug control method that replaces herbicide, and a bug repellent used therefor.

Written by Sawako Matsuzaki and Kazuo Takee City Pest Encyclopedia Asakura Shoten (1993)

  The problem to be solved by the present invention is to find a safe, simple, and effective stink bug repellent or control substance, to use this to repel or control stink bugs, and to develop a method for producing such a substance Was to do.

  The present inventors have conducted extensive research to solve the above-mentioned problems, isolated endophytes from grasses, identified compounds having stink bug repellent activity in their metabolites, and their derivatives have high stink bug repellent activity. As a result, the present invention has been completed.

（Ｉ）
［式中、ＲはＨ、Ｃ_１−６アルキル、ＣＯＣ_１−６アルキル、ＣＯＯＨまたはアリールであり、Ｘ、Ｙ、Ｚは独立して水素またはＣ_１−３アルキルである］で示される化合物を含む、カメムシ忌避剤；
（２）化合物が、式（ＩＩ）：

（ＩＩ）
［式中、ＲはＣＯＣ_１−３アルキル］で示される化合物である（１）記載のカメムシ忌避剤；
（３）カメムシが斑点米カメムシである（１）または（２）記載の忌避剤；
（４）式（Ｉ）：

（Ｉ）
［式中、ＲはＨ、Ｃ_１−６アルキル、ＣＯＣ_１−６アルキル、ＣＯＯＨまたはアリールであり、Ｘ、Ｙ、Ｚは独立して水素またはＣ_１−３アルキルである］で示される化合物をカメムシに適用することを特徴とする、カメムシの忌避方法；
（５）化合物が、式（ＩＩ）：

（ＩＩ）
［式中、ＲはＣＯＣ_１−３アルキル］で示される化合物である（４）記載のカメムシの忌避方法；
（６）カメムシが斑点米カメムシである（４）または（５）記載のカメムシの忌避方法；
（７）式（ＩＩ）：

（ＩＩ）
［式中、ＲはＣＯＣ_１−６アルキルである］で示される化合物の製造方法であって、下記工程：
（ａ）Biscogniauxia属の菌を培養し；
（ｂ）培養液を有機溶媒にて抽出し；
（ｃ）有機抽出画分から３−（４−メチル−フラン−３−イル）−プロパン−１−オールを得て；次いで
（ｄ）上記（ｃ）で得られた３−（４−メチル−フラン−３−イル）−プロパン−１−オールの８位の水酸基をエステル化する
を特徴とする製造方法；
（８）Biscogniauxia属の菌が、独立行政法人製品評価技術基盤機構 特許微生物寄託センター（ＮＰＭＤ）に受領番号ＮＩＴＥ ＡＰ−７９６として受領された菌である、（７）記載の製造方法。 That is, the present invention provides the following (1) to (8).
(1) Formula (I):

(I)
Wherein R is H, C _1-6 alkyl, COC _1-6 alkyl, COOH or aryl, and X, Y and Z are independently hydrogen or C _1-3 alkyl. Including stink bug repellent;
(2) the compound is of formula (II):

(II)
[Wherein R is a compound represented by COC _1-3 alkyl], a stink bug repellent according to (1);
(3) The repellent according to (1) or (2), wherein the stink bug is a spotted rice stink bug;
(4) Formula (I):

(I)
Wherein R is H, C _1-6 alkyl, COC _1-6 alkyl, COOH or aryl, and X, Y and Z are independently hydrogen or C _1-3 alkyl. A method for repelling stink bugs, characterized by applying to stink bugs;
(5) the compound is of formula (II):

(II)
[Wherein R is a compound represented by COC _1-3 alkyl], the method for repelling stink bugs according to (4);
(6) The stink bug repellent method according to (4) or (5), wherein the stink bug is a spotted rice stink bug;
(7) Formula (II):

(II)
[Wherein R is COC _1-6 alkyl], which is a method for producing a compound represented by the following steps:
(A) culturing a bacterium of the genus Biscogniauxia;
(B) extracting the culture solution with an organic solvent;
(C) 3- (4-methyl-furan-3-yl) -propan-1-ol was obtained from the organic extract fraction; then (d) 3- (4-methyl-furan obtained in (c) above -3-yl) -propan-1-ol, wherein the hydroxyl group at the 8-position is esterified;
(8) The production method according to (7), wherein the bacterium belonging to the genus Biscogniauxia is a bacterium that has been received as a receipt number NITE AP-796 by the National Institute of Technology and Evaluation (NPMD).

  According to the present invention, a safe, simple, and effective stink bug repellent or control material, a stink bug repellent or control method using the same, and a method for producing such a material are provided.

FIG. 1 is a diagram showing an outline of a repellent activity measuring apparatus for a stink bug repellent of the present invention. FIG. 2 is a diagram showing the results of examining the repellent activity of the stink bug repellent of the present invention. In the figure, compound 1, compound 2, compound 3, and compound 4 are derivative 1, derivative 2, derivative 3, and derivative 4 in the specification, respectively.

（Ｉ）
［式中、ＲはＨ、Ｃ_１−６アルキル、ＣＯＣ_１−６アルキル、ＣＯＯＨまたはアリールであり、Ｘ、Ｙ、Ｚは独立して水素またはＣ_１−３アルキルである］で示される化合物を含む、カメムシ忌避剤を提供する。 In one aspect, the present invention provides a compound of formula (I):

(I)
Wherein R is H, C _1-6 alkyl, COC _1-6 alkyl, COOH or aryl, and X, Y and Z are independently hydrogen or C _1-3 alkyl. A stink bug repellent is provided.

（ＩＩ）
［式中、ＲはＣＯＣ_１−６アルキルである］で示される化合物である。上記の好ましい式（ＩＩ）の化合物のうち、さらに好ましい化合物はＲがＣＯＣ_１−３アルキルである化合物である。 The compound which is an active ingredient of the stink bug repellent of the present invention is a compound represented by the above formula (I). Preferred compounds of formula (I) according to the invention are those in which R is COC _1-6 alkyl, X is methyl, Y and Z are hydrogen, ie formula (II):

(II)
[Wherein R is COC _1-6 alkyl]. Of the above preferred compounds of formula (II), more preferred are those in which R is COC _1-3 alkyl.

In the present specification, C _1-6 alkyl represents an alkyl group having 1 to 6 carbon atoms, and includes methyl, ethyl, propyl, butyl, pentyl and hexyl groups, and geometrical isomers thereof. C _1-3 alkyl represents an alkyl group having 1 to 3 carbon atoms, and includes methyl, ethyl and propyl, and geometric isomers thereof.

  Synthetic pesticides are problematic in terms of contamination of crops and soil, and residue in the environment including human livestock. Therefore, in the present invention, attention was paid to stink bug repellent substances in natural products. Furthermore, the use of repellents is thought to have less impact on the ecosystem than pesticides. In addition, it is more effective to control and prevent the inflow of stink bugs that come in succession by using repellents than to control and control them with insecticides. In the present invention, attention was paid to microorganisms symbiotic with plants in searching for naturally-derived substances. As a result, endophyte (microorganism living in a symbiotic manner in the plant) symbiotic to the grass family plant is a stink bug repellent substance 3- (4-methyl-furan-3-yl) -propane-1. It was found to produce ols (compounds where R = H in formula (II)). As described in the Examples, this endophyte was isolated from the grass family Enocologosa. Although 3- (4-methyl-furan-3-yl) -propan-1-ol itself has stink bug repellent activity, some of its derivatives have been found to have higher repellent activity.

  In the present specification, stink bugs refer to insects belonging to the order Hemiptera / Hemiptera. Such insects include, for example, insects of the stink bug family, dromedary family, nagamemushi family, and helicopterid family. The stink bug sucks and damages all crops. Therefore, the scope of application of the stink bug repellent of the present invention is all stink bugs that suck all crops, and stink bugs that suck grain (eg, rice, wheat, millet, barnyard millet, etc.) Spring gourd turtle, etc.), stink bugs that suck fruit trees (mandarin oranges, pears, apples, peaches, cherries, etc.) And other bugs, such as turtles, hoso-helical turtles, and terrestrial helicopter turtles, such as soybeans and other legumes (e.g. In particular, the repellent of the present invention is preferred against spotted rice stink bugs. About 60 kinds of spotted rice stink bugs are known, and examples thereof include red-bellied spider turtle, spider helicopter, red spider turtle, spider helicopter, southern stink bug, etc., but the stink bug repellent of the present invention. The scope of application is not limited to these stink bugs.

  The dosage form of the stink bug repellent of the present invention may be any, and may be solid (granular, powder, etc.), liquid (solution, suspension, etc.), and semi-solid (paste, etc.). The application mode / means of the stink bug repellent of the present invention may be any mode / means as long as it can repel stink bugs.For example, it is sprayed or applied to a plant, for example, using a sprayer. Spray or install near the plant by appropriate means, for example, install a felt or sponge soaked in the vicinity of the plant, or put the stink bug repellent of the present invention in a bottle etc. near the plant Installed on the ground where the stink bug repellent of the present invention is impregnated, installed on the ground where the plant is cultivated, suspended on a string stretched several tens of centimeters above the ground, hung directly on the plant foliage, etc. Examples of styles and means. A preferred application mode / means of the repellent of the present invention is a mode / means such that the drug does not directly touch the plant or the ground.

The application amount of the stink bug repellent of the present invention may be any application amount as long as it can repel stink bugs. Preferably, the application amount is such that it does not harm the plant itself, the surrounding environment and human livestock. And Examples of such an applied amount include an LD ₅₀ value obtained from an acute toxicity test, an amount calculated from a non-toxic amount obtained from a chronic toxicity test, and the like. A preferable application amount of the stink bug repellent of the present invention can be determined in consideration of toxicity tests and actual field effects.

  The stink bug repellent of the present invention may be used alone or in combination with other drugs such as biorepellent, biocide, insect repellent, insect repellent, insecticide and the like.

  In another aspect, the present invention provides a method for repelling stink bugs, which comprises applying the compound represented by formula (I) to stink bugs. Preferred compounds of formula (I), the scope of application of the method, the mode of application, and the amount of repellent applied in the method are as described above.

  In a further aspect, the present invention provides a process for producing a compound of formula (II). The method comprises culturing Biscogniauxia spp .; extracting the culture solution with an organic solvent; 3- (4-methyl-furan-3-yl) -propan-1-ol (hereinafter “MFP”) from the organic extract fraction. Then, the hydroxyl group at the 8-position of the compound of MFP obtained in the previous step is esterified.

  The bacteria of the genus Biscogniauxia to be used may be those that produce MFP, and preferably, as the receipt number NITE AP-796, on August 13, 2009 at the National Institute of Technology and Evaluation (NPMD) The received strain (referred to herein as Hs 259). The culture conditions may be either liquid culture or solid culture, and liquid culture is preferred from the viewpoint of mass production. Culture conditions for filamentous fungi known to those skilled in the art can be used. A person skilled in the art can appropriately select a culture apparatus and the like. When liquid culture | cultivation of H-s259 bacteria, you may culture | cultivate still at 20-28 degreeC for 10 to 20 days with a malt leaching medium.

  The obtained culture is extracted with an organic solvent (or a mixture of organic solvents) such as acetone, ethyl acetate, and n-hexane to obtain an organic extract fraction. These operations are known to those skilled in the art. Purification and isolation of MFP from the obtained organic extract fraction can also be performed by means and methods known to those skilled in the art. For example, the MFP may be purified and isolated by silica gel column chromatography using an organic solvent such as acetone, ethyl acetate, n-hexane, or a mixture thereof as an elution solvent.

  The compound of formula (II) of the present invention can be obtained by esterifying the hydroxyl group at the 8-position of the obtained MFP by means and methods known to those skilled in the art. The production method of the compound of the formula (II) of the present invention is not limited to the above method, and can be synthesized by methods known to those skilled in the art. Chemical synthesis methods for MFP are also known to those skilled in the art.

  EXAMPLES Hereinafter, the present invention will be described more specifically and in detail with reference to examples. However, the examples are merely illustrative and should not be construed as limiting the present invention.

Example 1: Isolation and identification of endophytes Gramineae wild grasses collected at various sites in Tottori University were collected. The leaf part and the leaf sheath part were cut into pieces of about 5 mm. These sections were immersed in 100% ethanol for 1 minute in a clean bench to dissolve the wax on the plant tissue surface. The surface was then sterilized by stirring in a 3-5% sodium hypochlorite solution for 1-5 minutes. This was washed three times with sterilized water, finely chopped with a sterilized razor, and a malt solid medium for searching for filamentous fungi prepared in a plastic petri dish (50 g of malt extract, 30 g of glucose, 3 g of peptone, 20 g of agar, 50 mg of streptomycin per 1 L of water) ). This was cultured at 24 ° C. Bacteria grown from the vicinity of the cut end of the plant tissue are sequentially replanted into a new malt solid medium, and when the bacteria become single, a malt slope medium (50 g of malt extract, 30 g of glucose, 3 g of peptone, 20 g of agar) is added to 1 L of water. separated.

  The separated endophyte was inoculated into a malt leaching medium and cultured at 24 ° C. for 7 days. After culturing, the filtrate and cells were separated by sucking and drinking, and extracts were obtained from each. About these extracts, the repellent activity test demonstrated in Example 2 was done, and the thing with strong repellent activity was searched. As a result, we found a particularly strong repellent activity in the culture filtrate of endophyte isolated from entomologosa collected at Tottori University campus. This endophyte was named H-s259.

  When H-s 259 bacteria were inoculated into malt agar medium and PDA agar medium and cultured at 24 ° C. for 7 days, white fluffy flora was formed and no spore formation was observed. DNA was extracted from H-s 259 bacteria and sequenced for the ITS region of rDNA. When the homologous search by BLAST of DDBJ was performed on the determined sequence, 92% homology to Biscogniauxia atropunctata was confirmed in the nuclei of Ascomycota subsp. One strain was identified. Hs 259 bacteria were received on August 13, 2009 by the National Institute of Technology and Evaluation (NPM), the National Institute for Product Evaluation Technology (NPMD), and given the receipt number NITE AP-796.

Example 2: Identification of repellent substance produced by H-s 259 bacteria H-s 259 bacteria were inoculated into 10 L of malt leaching medium and cultured at 24 ° C. for 14 days. This culture filtrate was extracted with ethyl acetate to obtain an extract. This extract was refined using repellent activity as an index. The extract was fractionated by silica gel column chromatography using acetone and n-hexane as an elution solvent, and a very strong repellent activity was observed in the fraction eluted with 10% acetone in n-hexane. This fraction was subjected to silica gel flash column chromatography using water-containing ethyl acetate in n-hexane as an elution solvent, and the fraction showing strong repellent activity was fractionated by silica gel thin layer chromatography to obtain a fraction showing strong repellent activity. . This was fractionated by HPLC to obtain a colorless oily compound (Compound A). Compound A fluoresced under UV (254 nm) irradiation. Tables 1 and 2 show the instrumental analysis data of Compound A. ^A JOEL JMN-ECP500 NMR spectrometer was used for ¹ H NMR and ¹³ C NMR, a JOEL AX-505HA spectrometer was used for mass spectrometry, and Shimadzu SPD-6A liquid chromatography was used for HPLC.

From these results, Compound A was identified as 3- (4-methyl-furan-3-yl) -propan-1-ol (abbreviated as MFP). The structural formula of the MFP is shown below.

The repellent activity of MFP was examined using Marshirahoshikamemushi. The test method for repellent activity is described below.
(A) Test insect Marshirahoshikamemushi collected outdoors was placed in a desiccator planted with gramineous plants such as damselfly and Oshihiba as feed, and reared at room temperature.

(B) Assembly of test apparatus A 9 cm diameter polyvinyl chloride tube and a plastic petri dish (1.5 × 9 cm) lid were prepared. The polyvinyl chloride tube was straightly cut at a height of 2 cm and 4 cm. Black paper and filter paper were prepared by cutting them into a 9 cm diameter circle.
(B-1) Assembly of the upper part of the test apparatus A thin piece of silicon grease was applied to the inner wall of a polyvinyl chloride pipe cut into 2 cm in order to prevent stink bug scalp. The mouth of the test tube (φ1 cm) was heated with a gas burner and pressed to a position 1 cm from the end of the plastic petri dish to make a hole. The filter paper also had a 1 cm diameter hole 1 cm from the edge. This filter paper was laid on a plastic petri dish so that the holes overlapped, and a polyvinyl chloride tube coated with silicon grease was placed. I wrapped vinyl tape around the wall of a plastic petri dish several times to prevent light from entering.
(B-2) Assembly of lower part of test apparatus A black paper was laid on a plastic petri dish, and a polyvinyl chloride tube cut into 4 cm was placed. I wrapped vinyl tape around the wall of a plastic petri dish several times to prevent light from entering.
The upper and lower parts of the test apparatus were combined and used after confirming that there was no gap. The structure of the test apparatus is shown in FIG.

(C) Repellent activity test method A section of filter paper cut to 0.5 × 4 cm was inserted into a φ1 × 3.5 cm sample tube, and 50 μL of a sample dissolved in acetone was dropped using a syringe or the like and soaked. As a control, 50 μL of acetone alone was prepared, and the two were air-dried for 30 minutes to remove acetone. Thereafter, the sample tube containing the sample and filter paper was inserted into the hole of the test apparatus. Next, 20 Marshirashi stink bugs kept in a φ3.5 x 1 cm petri dish coated with silicon grease, placed upside down between the holes of the test equipment, and artificially installed the test equipment without removing the petri dish. Put in the center of the meteorological instrument. The temperature inside the artificial weather device was set to 10 ° C., and all lights were attached. After waiting for 3 minutes to stabilize the stink bug, the petri dish was removed and the test was started. The number of insects in both sample tubes and the number of insects out were recorded in one test 30 minute cycle. This operation was repeated 4 times. In addition, in order to make the conditions uniform, the holes on the sample administration side and the control side were alternately changed for testing. The repellent degree was calculated by the following formula.
Repellency = {[(C / C + T) X100] −50} X2
C: Number of insects in control sample tube T: Number of insects in sample tube on sample administration side Average repellency and standard error of 4 tests were calculated. The number of insects that were not in the sample tube after the test was ignored.

Table 3 shows the repellent activity of naphthalene and MFP. Naphthalene showed strong repellent activity at 0.5 mg, but no repellent activity at 0.1 mg. MFP showed a strong repellent activity exceeding a repellent degree of 50 even at 0.1 mg. MFP showed stronger repellent activity than naphthalene even at 0.5 mg. Considering these results and the molecular weight of each compound, it was found that MFP has a stronger repellent activity than naphthalene which is a positive control.

誘導体１（式（ＩＩ）においてＲ＝ＣＯＣＨ_３）

誘導体２（式（ＩＩ）においてＲ＝ＣＯＣ_２Ｈ_５）

誘導体３（式（ＩＩ）においてＲ＝ＣＯＣ_３Ｈ_７）

誘導体４（式（ＩＩ）においてＲ＝ＣＯＣ_６Ｈ_５） Example 3 Synthesis of MFP Derivative The following derivatives were synthesized.

Derivative 1 (R = COCH ₃ in formula (II))

Derivative 2 (R = COC ₂ H ₅ in formula (II))

Derivative 3 (R = COC ₃ H ₇ in formula (II))

Derivative 4 (R = COC ₆ H ₅ in formula (II))

(1) Preparation of MFP A 200 mL malt leaching medium was prepared in a 500 mL Erlenmeyer flask. H-s 259 bacteria were inoculated into 50 of this medium and statically cultured at 24 ° C. for 14 days. After completion of the culture, the filtrate was separated into cells. 10 L of this culture filtrate was adjusted to around pH 2 with 6M hydrochloric acid. This was extracted three times with ethyl acetate to obtain an extract. Anhydrous sodium sulfate was added to the extract and left overnight to dehydrate. This was concentrated under reduced pressure to obtain a filtrate extract. This extract was dissolved in acetone, and 30.5 g of Daisogel IR-60 was added. The extract was adsorbed on a gel, and this was placed on a column (φ6.2 × 72 cm) of Daisogel IR-60 (φ88 / 125 μm) and subjected to silica gel dry column chromatography. As an elution solvent, n-hexane containing 0, 5, 10, 20, 30, 100% (v / v) acetone was used. 8 L of each solvent was flowed, and the eluate was concentrated under reduced pressure. 200 mg of a 10% fraction was dissolved in acetone, 1 g of celite was added, and the mixture was concentrated and adsorbed under a nitrogen stream. This was placed on a column (φ3 × 39 cm) of Wakogel FC-40 (φ20-40 cm) and subjected to silica gel flash column chromatography. As an elution solvent, water containing n-hexane containing 0, 5, 10, 20, 30, 100% (v / v) ethyl acetate was used. Each 200 mL of the solvent was allowed to flow, and 10 mL each was dispensed into 20 test tubes, which were concentrated under reduced pressure. Each obtained fraction was subjected to silica gel thin layer chromatography using n-hexane containing 50% ethyl acetate as a developing solvent. Fractions having similar spots under UV (254 nm) irradiation were combined to obtain MFP in 20% fraction 1-9. In order to obtain a high-purity MFP for assay, it was fractionated by HPLC. A fraction having a retention time of 29 minutes was extracted with ethyl acetate to obtain a highly pure MFP. Table 4 shows the HPLC conditions.

(2) Synthesis of Derivative 1 MFP (10.1 mg) was dissolved in 500 μL of pyridine, 500 μL of acetic anhydride was added, and reacted at room temperature overnight. Distilled water containing ice was adjusted to pH 2 with 6M hydrochloric acid while stirring with a stirrer, and the reaction solution was added dropwise and stirred for 1 hour. After stirring, the mixture was extracted 3 times with ethyl acetate. After extraction, the ethyl acetate layer was washed with 1M sodium hydrogen carbonate and then washed three times with a small amount of saturated brine. After washing, anhydrous sodium sulfate was added and left overnight. The following day, concentration under reduced pressure yielded derivative 1 (8.9 mg), a colorless oily substance having an Rf value of 0.27.
The NMR data and MS data of derivative 1 are shown in Table 5.

(3) Synthesis of Derivative 2 MFP (9.5 mg) was dissolved in 1 mL of dry acetone and stirred with a stirrer. Pyridine (2N, 11.3 mg) was added thereto, and propionyl chloride (2N, 12.9 mg) was added dropwise, and the mixture was allowed to react overnight at room temperature with stirring. The next day, it was extracted three times with ethyl acetate. After extraction, the ethyl acetate layer was washed with 1M sodium hydrogen carbonate and then washed three times with a small amount of saturated brine. After washing, anhydrous sodium sulfate was added and left overnight. The solution was concentrated under reduced pressure on the next day, and the extract (8.1 mg) was fractionated by silica gel thin layer chromatography using n-hexane containing 30% ethyl acetate as a developing solvent to obtain each fraction. The fraction with an Rf value of 0.61 was extracted with hydrous ethyl acetate to obtain derivative 2 (7.6 mg).
The NMR data and MS data of derivative 2 are shown in Table 6.

(4) Synthesis of Derivative 3 MFP (9.7 mg) was dissolved in 1 mL of dry acetone and stirred with a stirrer. Pyridine (4N, 22.6 mg) was added thereto, butyryl chloride (4N, 29.8 mg) was added dropwise, and the mixture was reacted overnight at room temperature with stirring. The next day, it was extracted three times with ethyl acetate. After extraction, the ethyl acetate layer was washed with 1M sodium hydrogen carbonate and then washed three times with a small amount of saturated brine. After washing, anhydrous sodium sulfate was added and left overnight. The solution was concentrated under reduced pressure on the next day, and the extract (10.6 mg) was fractionated by silica gel thin layer chromatography using n-hexane containing 30% ethyl acetate as a developing solvent to obtain each fraction. The fraction with an Rf value of 0.57 was extracted with hydrous ethyl acetate to obtain derivative 3 (4.0 mg).
The NMR data and MS data of derivative 3 are shown in Table 7.

(5) Synthesis of Derivative 4 MFP (11.5 mg) was dissolved in 1 mL of dry acetone and stirred with a stirrer. Pyridine (3N, 18.9 mg) was added thereto, butyryl chloride (3N, 33.7 mg) was added dropwise, and the mixture was reacted overnight at room temperature with stirring. The next day, it was extracted three times with ethyl acetate. After extraction, the ethyl acetate layer was washed with 1M sodium hydrogen carbonate and then washed three times with a small amount of saturated brine. After washing, anhydrous sodium sulfate was added and left overnight. The solution was concentrated on the next day under reduced pressure, and the extract (24.5 mg) was fractionated by silica gel thin layer chromatography using n-hexane containing 30% ethyl acetate as a developing solvent to obtain each fraction. The fraction with an Rf value of 0.57 was extracted with hydrous ethyl acetate to obtain derivative 4 (7.4 mg).
The NMR data and MS data of derivative 4 are shown in Table 8.

  From the NMR spectrum and MS spectrum data, the correctness of the chemical structures of the synthesized derivatives 1 to 4 was confirmed.

Example 4: Repellent activity of the compound of the present invention As described in Example 2, the repellent activity of derivatives 1-4, MFP and naphthalene synthesized in Example 3 was examined. The results are shown in FIG. Derivative 1, Derivative 2, and Derivative 3 had stronger repellent activity than MFP. Derivative 1 showed the highest repellent activity, followed by Derivative 2, Derivative 3, and MFP in the order of repellent activity. From these results, it was recognized that when the hydroxyl group at the 8-position is esterified, the repellent activity tends to increase. This shows that the hydroxyl group at the 8-position is not essential for the repellent activity. However, since derivative 4 has a repellent activity weaker than that of MFP, a tendency to weaken the repellent activity was observed when the hydroxyl group was benzoylated. The reason why the repellent activity of the derivative 1 was particularly strong even at a dose of 0.1 μmol is considered to be due to its high volatility.

Example 5: Application example in the field A thick and strong filter paper piece (1 × 5 cm) was impregnated with 0.1 mL of a derivative 1 acetone solution (2 mg / L) per sheet. A small hole was made in one end of the filter paper piece, and a thin wire was passed through it. This was applied to about 4 ripening rice stalks and leaves per m ² to control spotted rice stink bugs.

  The present invention can be used in the field of agriculture, especially in the field of cultivating vegetables and fruit trees, and in the field of agricultural chemicals, particularly in the field of manufacturing pest repellents.

Receipt Number NITE AP-796
Received on August 13, 2009 by the National Institute for Microbiology (NPMD), National Institute of Technology and Evaluation.

Claims (8)

Formula (I):

(I)
Wherein R is H, C _1-6 alkyl, COC _1-6 alkyl, COOH or aryl, and X, Y and Z are independently hydrogen or C _1-3 alkyl. Contains stink bug repellent. The compound is of formula (II):

(II)
The stink bug repellent according to claim 1, which is a compound represented by the formula: wherein R is COC _1-3 alkyl.   The repellent according to claim 1 or 2, wherein the stink bug is a spotted rice stink bug. Formula (I):

(I)
Wherein R is H, C _1-6 alkyl, COC _1-6 alkyl, COOH or aryl, and X, Y and Z are independently hydrogen or C _1-3 alkyl. A method for repelling stink bugs, which is applied to stink bugs. The compound is of formula (II):

(II)
The method for repelling stink bugs according to claim 4, wherein R is a compound represented by COC _1-3 alkyl.   6. The stink bug repellent method according to claim 4 or 5, wherein the stink bug is a spotted rice stink bug. Formula (II):

(II)
[Wherein R is COC _1-6 alkyl], which is a method for producing a compound represented by the following steps:
(A) culturing a bacterium of the genus Biscogniauxia;
(B) extracting the culture solution with an organic solvent;
(C) 3- (4-methyl-furan-3-yl) -propan-1-ol was obtained from the organic extract fraction; then (d) 3- (4-methyl-furan obtained in (c) above -3-yl) -propan-1-ol is produced by esterifying the hydroxyl group at the 8-position.   8. The production method according to claim 7, wherein the bacterium belonging to the genus Biscogniauxia is a bacterium that has been received as a receipt number NITE AP-796 by the National Institute of Technology and Technology (NPMD).

Images