KR20210127485A - Composition for controlling Geometrid moth, method for preparing the same, and method for controlling Geometrid moth using the same - Google Patents

Abstract

Provided are a composition for controlling geometer moths which comprises henicosapentaene, a method for preparing the composition for controlling geometer moths, a trap for controlling geometer moths, a method for controlling geometer moths, and a method for monitoring geometer moths. Accordingly, the present invention can be used for environmental-friendly pest control which monitors and detects the occurrence density of geometer moths, and lowers the density of pests through mass capture or copulation disturbance.

Description

Composition for controlling Geometrid moth, method for controlling the same, and method for controlling moth using the same

It relates to a composition for controlling moths, a method for preparing the same, a method for controlling moths using the same, and a method for monitoring moths.

Geometrid moth is the generic name for the Lepidoptera family. In the larval state, it crawls while crawling and unfolding, forming a twig-like shape that hides itself. Among the moths, Naxa seriaria is a pest belonging to the family Moth, which mainly injures plants of the ash family, such as oleifera, ash, dogwood, and lilac. Recently, a sudden mass outbreak of cobwebs is applied to branches and leaves, which not only hinders the growth of trees, but also greatly damages the aesthetic value of landscape trees.

Sex pheromone is a kind of insect behavior control substance used by insects, and in the case of butterflies, it is mainly released by females and males who respond to it are attracted to mate. Adult pheromone is a tool that can be used effectively in the monitoring of pests, and provides very accurate information on the timing and density of adult worms through a small amount of treatment. In addition, when using a sex pheromone trap, it can be used as an environmentally friendly pest control method such as lowering the density through mass capture of males, developing a mating disruptor to lower the mating probability, or lowering the density of pests. In general, different compound(s) for each insect species is used as a sex pheromone, or when using the same type of compound, the composition ratio is changed and used as a sex pheromone.

Therefore, in order to control the moth in an environmentally friendly way, it is necessary to detect the sex pheromone of the moth and develop a control method using the same.

W. S. Leal et al., Naturwissenschaften volume 92, pp. 139-146 (2005)

A composition for controlling moths is provided.

A method for preparing a composition for controlling moths is provided.

Provides traps for moth control.

A method of controlling moths is provided.

A method for monitoring moths is provided.

One aspect provides a composition for controlling moths containing henicosapentaene (heneicosapentaene).

The henicosapentaene is an unsaturated hydrocarbon compound having 21 carbon atoms and 5 double bonds. The henicosapentaene may be (3Z,6Z,9Z,12Z,15Z)-henicosapentaene. The henicosapentaene may be a natural extract or a synthetic compound. The henicosapentaene may be synthesized by an organic synthesis method.

The henicosapentaene may be a pheromone. The term "pheromone" refers to a substance secreted or released by an animal, such as an insect, used for communication between animals of the same species. The pheromone is a sex pheromone, aggregation pheromone, alarm pheromone, trail pheromone, epiideictic pheromone, releaser pheromone, primer pheromone, signal pheromone , and may be selected from the group consisting of territorial pheromones. The henicosapentaene may be a sex pheromone.

The moth (Geometrid moth) is an insect belonging to the Lepidoptera family (Geometridae). The caterpillar of the moth is a caterpillar that crawls while retracting and unfolding in the larval state. The moths are the early spring subfamily Archearinae, Ennominae, Winter Alsophilinae, Oenochrominae, Orthostixinae, Geometrinae, Arabidopsis moth Sterrhinae), or an insect of the subfamily Larentiinae. The moth may be an insect of the genus Naxa of the subfamily Orthostixinae. The peony moth may be a caterpillar moth ( Naxa seriaria ).

Controlling (or management) means to prevent or minimize damage to biological species such as insects or pathogens. The control may be biological control, chemical control, agronomic control, physical control, or a combination thereof. The biological control may be control using a pheromone. The biological control may be a population survey (monitoring), mass trapping (mass trapping), or mating disruption (mating disruption).

The composition may attract or trap moths. The composition is capable of attracting or trapping male moths. The moth may be an adult male. The composition can control the male moth by lowering the reproduction rate by catching the male moth.

The composition may be formulated as a pesticide or pesticide formulation. The formulation of the composition may be selected from the group consisting of rubber septum, sachet, capsule, gel, emulsion, suspension, emulsion, paste, cream, oil, powder, wax, and spray.

The composition may include excipients or additives. The composition may include a plasticizer, a colorant, a brightener, a surfactant, a dispersant, an emulsifier, a glidant, or a combination thereof.

Another aspect is a first step of producing icosapentaen-1-ol from ethyl-icosapentaenoate (ethyl-icosapentaenoate); a second step of producing icosapetaene-1-yl 4-methylbenzenesulfonate from icosapentaen-1-ol; and a third step of producing henicosapentaene from icosapentaen-1-yl 4-methylbenzenesulfonate.

Henicosapentaene is as described above.

The composition may be a composition for controlling moths according to an aspect.

The method comprises a first step of producing icosapentaen-1-ol from ethyl-icosapentaenoate. Ethyl-icosapentaenoate may be ethyl(5Z,8Z,11Z,14Z,17Z)-icosapentaenoate. The first step may be performed in the presence of any one or more of lithium aluminum hydride (LAH) and tetrahydrofuran (THF).

The method comprises a second step of producing icosapetaene-1-yl 4-methylbenzenesulfonate from icosapentaen-1-ol. The icosapentaen-1-yl 4-methylbenzenesulfonate may be (5Z,8Z,11Z,14Z,17Z)-icosapentaen-1-yl 4-methylbenzenesulfonate. The second step may be performed in the presence of any one or more of para-toluenesulfonyl chloride (TsCl) and pyridine.

The process comprises a third step of producing henicosapentaene from icosapentaen-1-yl 4-methylbenzenesulfonate. Henicosapentaene may be (3Z, 6Z, 9Z, 12Z, 15Z)-henicosapentaene. The third step may be performed in the presence of at least one of methylmagnesium bromide (CH ₃ BrMg) and a dilithium tetrachlorocuprate (II) solution (Li ₂ CuCl _{4 ).}

The method may further include performing washing, concentration, purification, or a combination thereof.

Another aspect provides a trap for controlling moths comprising henicosapentaene.

The henicosapentaene, moth, and control are the same as described above.

The trap may be henicosapentaene or a composition for controlling moths containing the same by dripping, leaving, applying, spraying, or a combination thereof.

The trap may be a trap for controlling pests. The trap includes a delta-trap, a bucket-trap, a sticky trap, a fish-net trap, a tetragonal trap, a beetle trap, and a trap. It may be a water trap, a cone trap, a light trap, an electric shock trap, or a combination thereof. The delta trap may be a trap in which the control composition is located on the inside of the triangular prism. The bucket trap may also be referred to as a funnel trap or a unittrap.

Another aspect provides a method for controlling moths, comprising the step of dripping, leaving, spraying, applying, or a combination thereof, a composition comprising henicosapentaene.

The henicosapentaene, composition, moth, and control are the same as described above.

In the method, by dripping, leaving, spraying, applying, or a combination thereof, a composition containing henicosapentaene is carried out to capture and control the moth.

Another aspect provides a method for monitoring moth moths, comprising the step of leaving, spraying, applying a composition comprising henicosapentaene, or performing a combination thereof.

The method can be used to determine the control method and target area by monitoring the appearance time, the occurrence density, or a combination of the moths.

Since henicosapentaene has a high attractiveness to moths, for example, lichen moth, a composition for controlling moths containing henicosapentaene, a method for preparing a composition for controlling moths, traps for controlling moths, The moth control method and the moth monitoring method can be used for environmentally friendly pest control by identifying the monitoring and occurrence density of the black moth, and lowering the density of pests through mass capture or yeast disturbance.

1 is a schematic diagram of connection of gas chromatography-electroantennographic detection (GC-EAD) for electrophysiological stimulation measurement.
Figure 2 is a chromatogram of the extract of pheromone glands of the pharyngeal moth.
3 is a chromatogram of an electrophysiological response of a male to an extract of a female pheromone gland of a larvae moth.
4 is a flow diagram for the synthesis of (3Z,6Z,9Z,12Z,15Z)-henicosapentaene.
5 is a chromatogram of artificially synthesized sex pheromone (3Z, 6Z, 9Z, 12Z, 15Z)-henicosapentaene.
6 is a mass spectrum (m/z) of pheromone gland extract (top) and artificially synthesized sex pheromone (3Z, 6Z, 9Z, 12Z, 15Z)-henicosapentaene (bottom).
7 is an electroantennogram (EAG) connection schematic diagram for measuring electrophysiological stimulation.
8 is a graph of the male electrophysiological response to the treatment amount of the sex pheromone (3Z, 6Z, 9Z, 12Z, 15Z)-henicosapentaene.
9 is a schematic diagram of a bucket trap (A) and a delta trap (B) used in the experiment.
10 is a graph of the average number of insects captured per trap as a function of (3Z, 6Z, 9Z, 12Z, 15Z)-henicosapentaene throughput.
11 is a graph of the average number of insects captured per trap according to pheromone trap types.

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

Example 1. Extraction and analysis of female adult pheromones

For the test larvae used in the experiment, larvae (about 2nd to 3rd instars) collected from Mt. 75 (37°46'06.5"N 127°53'52.3"E), Seongdong-ri, Bukbang-myeon, Hongcheon-gun, Gangwon-do were used by fugitive in the laboratory (temperature 25 °C, photoperiod 16L:8D). The young larvae were divided into males and females, and individually reared in an insect breeding container (diameter = 9.5 cm, height = 4 cm). Emerging adults were fed an aqueous solution of 5% (w/v) ascorbic acid and 3% (w/v) sucrose as food.

For the analysis of pheromone components, pheromone glands of female adults 3 days after hatching were extracted (n=107). The pheromone was extracted by immersion in hexane (hexane) of 10 μl per animal for 3 minutes. The extracted material was concentrated using nitrogen gas and then identified using gas chromatography (Agilent 7890A) equipped with a mass spectrometer (Agilent 5975C MSD). Gas chromatography-electroantennographic detection (GC-EAD) was used to search for substances that induce an electrophysiological response to male genus moth among pheromone gland extracts (FIG. 1). The instrument conditions used for the analysis are as follows.

GC-MS: injection (heater: 25°C, injection mode: Splitless, 15 mL/min at 0.75 min), column (HP-5MS semivolatile column; 30 m × 0.25 mm id, 0.25 μm film thickness, J&W Scientific, Folsom, CA, USA), oven (start: 40°C; #1: ramp at 30°C/min to 190°C; #2: ramp at 10°C/min to 215°C, hold for 5 min; #3: 320 Rise to °C at 10 °C/min), Aux (280 °C), Ionization (70 eV, 230 °C), Scan Range (41-400 amu)

GC-EAD: Injection (Heater: 200° C., Injection Mode: Splitless, 15 mL/min at 0.75 min), Column (DB-5MS column; 30 m × 0.25 mm id, 0.25 μm film thickness, J&W Scientific, Folsom, CA) , USA), oven (start: 40°C; #1: ramp at 10°C/min to 250°C; #2: ramp at 30°C/min to 320°C), detector (heater: 250°C, gas flow: 350 mL /min; H ₂ fuel flow: 35 mL/min; makeup (N ₂ ) flow: 25 mL/min).

Fig. 2 shows the chromatogram of the pheromone gland extract of the genus oleracea moth, and Fig. 3 shows the chromatogram of the male electrophysiological response to the female pheromone gland extract.

As a result of the analysis of FIGS. 2 and 3 , it was confirmed that the substance causing the electrophysiological reaction was (3Z,6Z,9Z,12Z,15Z)-heneicosapentaene. EI-MS m/z of (3Z,6Z,9Z,12Z,15Z)-henicosapentaene is 79 (100) [C ₆ H ₇ ] ⁺ , 91 (68) [C ₆ H ₅ -CH ₂ ] ⁺ , 67 (49) [C ₅ H ₇ ] ⁺ , 55 (47) [C ₄ H ₇ ] ⁺ , 77 (26) [C ₆ H ₅ ] ⁺ , 69 (19) [C ₅ H ₉ ] ⁺ , 93 (21) [C ₇ H ₉ ] ⁺ , 57 (26) [C ₄ H ₉ ] ⁺ , 105 (25) [C ₆ H ₅ -CH ₂ CH ₂ ] ⁺ and 80 (23) [C ₆ H ₈ ] ⁺ was.

Example 2. The sex pheromone (3Z, 6Z, 9Z, 12Z, 15Z) - Henicosapentaene synthesis

(3Z,6Z,9Z,12Z,15Z)-Henicosapentaene, the sex pheromone of the moth moth, was experimentally synthesized as follows. A flowchart for the synthesis of (3Z,6Z,9Z,12Z,15Z)-henicosapentaene is shown in FIG. 4 .

Using the starting material ethyl (5Z,8Z,11Z,14Z,17Z)-icosapentaenoate [Ethyl (5Z,8Z,11Z,14Z,17Z)-icosapentaenoate] (Compound 1 ), the intermediate (5Z ,8Z,11Z,14Z,17Z)-icosapentaen-1-ol[(5Z,8Z,11Z,14Z,17Z)-icosapentaen-1-ol](Compound 2 ), (5Z,8Z,11Z,14Z ,17Z)-icosapetaene-1-yl 4-methylbenzenesulfonate [(5Z,8Z,11Z,14Z,17Z)-icosapetaene-1-yl 4-methylbenzenesulfonate] (Compound 3 ) was synthesized. (5Z,8Z,11Z,14Z,17Z)-Icosapentaen-1-yl 4-methylbenzenesulfonate and methylmagnesium bromide reacted (3Z,6Z,9Z,12Z,15Z)-Henicosapentaene ( Figure 4, Compound 1 ) was synthesized (Figure 4).

Specifically, in order to synthesize (5Z,8Z,11Z,14Z,17Z)-icosapentaen-1-ol (Compound 2 ), in anhydrous tetrahydrofuran (Tetrahydrofuran: THF, 250 ml) at about -15 ° C. Lithium Aluminum Hydride (LAH, 4.82 g) was added. A solution of ethyl (5Z,8Z,11Z,14Z,17Z)-icosapentaenoate (compound 1 , 30 g, 90.770 mmol) diluted in 250 mL of THF was added to the reactor over about 1 hour. The mixture was heated naturally, stirred at room temperature for about 12 hours, and then the reaction was terminated. After cooling the internal temperature of the mixture to about -10°C, the reaction product was diluted with 200 ml of diethyl ether, and 5 ml of water was slowly added thereto. Then, 5 ml of a 15% (w/v) aqueous caustic soda solution was added to the mixture. After stirring at room temperature for about 30 minutes, the white salt was removed by filtration, and the filtrate was dried over anhydrous magnesium sulfate. The solvent was concentrated with a vacuum distiller, and purified by silica gel column to obtain (5Z,8Z,11Z,14Z,17Z)-icosapentaen-1-ol (Compound 2 , 25.0 g) (yield 83.0%). ¹ H-NMR (400 MHz, CDCl ₃ ): δ 5.20-5.40 (m, 10H), 3.60 (m, 2H), 2.87-2.65 (m, 8H), 2.15-1.95 (m, 4H), 1.58 (m) , 3H), 1.42 (m, 2H), 0.94 (t, 3H).

To synthesize (5Z,8Z,11Z,14Z,17Z)-icosapentaen-1-yl 4-methylbenzenesulfonate (Compound 3 ), pyridine (13.71 g) and (5Z,8Z,11Z, 14Z,17Z)-icosapentaen-1-ol (Compound 2 , 25.0 g) was dissolved in 300 ml of dichlormethane. Para-toluenesulfonyl chloride (p-Toluenesulfonyl chloride: TsCl, 24.78 g) was dissolved in 150 ml of dichloromethane and then added using a dropping funnel. After the reaction was carried out at room temperature for about 1 day, dichloromethane was removed by concentration under reduced pressure. The remaining compound was dissolved in 200 ml of ethyl acetate, washed and separated using distilled water. Thereafter, moisture was removed from the organic layer using a saturated aqueous sodium chloride solution and anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure and purified by silica gel column to obtain (5Z,8Z,11Z,14Z,17Z)-icosapentaen-1-yl 4-methylbenzenesulfonate (Compound 3 , 18.2 g) (yield 72.8). %). ¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.76 (d, J = 8.2 Hz, 2H), 7.32 (d, J = 8.1 Hz, 2H), 5.28-5.36 (m, 10H), 4.00 (t, J = 6.4Hz, 2H), 2.83-2.72 (m, 8H), 2.43 (s, 3H), 2.07-1.97 (m, 4H), 1.63 (m, 2H), 1.37 (m, 2H), 0.95 (t) , J = 7.5 Hz, 3H).

Finally, to synthesize (3Z,6Z,9Z,12Z ,15Z)-henicosapentaene (Compound 1 ), (5Z,8Z,11Z,14Z,17Z)-icosapentaen-1-yl 4- After dissolving methyl benzene sulfonate (Compound 3 , 2.0 g) in THF, methyl magnesium bromide (CH ₃ BrMg, 2.99 g) and dilithium tetrachlorocuprate (II) solution (Dilithium tetrachlorocuprate: Li _{2 ) at about -15°C} CuCl ₄ , 4.4 g) was added and reacted for about 40 minutes, and further reacted for about 2 hours at room temperature. After terminating the reaction by adding a saturated aqueous solution of ammonium chloride (NH ₄ Cl), it was concentrated using a reduced pressure concentrator. The concentrated material was dissolved again in 200 ml of ethyl acetate, and distilled water was added thereto, followed by washing and separation. Thereafter, water was removed using a saturated aqueous sodium chloride solution and anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column to obtain (3Z,6Z,9Z,12Z,15Z)-henicosapentaene (Compound 1 , 1.23 g). (yield 61.3%).

The chromatogram of artificially synthesized sex pheromones (3Z, 6Z, 9Z, 12Z, 15Z)-henicosapentaene is shown in FIG. , 15Z) - The mass spectrum (m/z) of henicosapentaene (bottom) is shown in FIG. 6 . ¹ H-NMR (400 MHz, CDCl ₃ ): δ 5.35-5.33 (m, 10H), 2.81-2.77 (m, 8H), 2.04-2.00 (m, 4H), 1.26-1.25 (m, 8H), 0.94 (t, 3H), 0.85 (t, 3H), EI-MS m/z is 79 (100) [C ₆ H ₇ ] ⁺ , 91 (64) [C ₆ H ₅ -CH ₂ ] ⁺ , 67 (54) ) [C ₅ H ₇ ] ⁺ , 80 (48) [C ₆ H ₈ ] ⁺ , 93 (29) [C ₇ H ₉ ] ⁺ , 77 (34) [C ₆ H ₅ ] ⁺ , 55 (32) [ C ₄ H ₇ ] ⁺ , 105 (29) [C ₆ H ₅ —CH ₂ CH ₂ ] ⁺ and 81 (22) [C ₆ H ₉ ] ⁺ .

As shown in FIGS. 5 and 6 , it was confirmed that the artificially synthesized sex pheromone (3Z, 6Z, 9Z, 12Z, 15Z)-henicosapentaene was the same as the compound extracted from the pheromone glands of A. moth pheromone.

Example 3. Sexual pheromone (3Z, 6Z, 9Z, 12Z, 15Z) - Confirmation of the electrophysiological response to the male star moth according to the amount of henicosapentaene treatment

A glass tube (Ø 1.5 mm, L75 mm) filled with 0.1 N KCL was in contact with the left antenna of the specimen, and electrolytically polished tungsten was connected through the right eye of the specimen (Fig. 7).

The sex pheromone [(3Z,6Z,9Z,12Z,15Z)-heneicosapentaene] was injected into the antennae for 1.5 seconds using a stimulation regulator (CS-55, syntech, Germany), and the generated stimulation was performed using a 4-channel IDAC system (syntech, Germany) and Auto spike (V3.0, syntech, Germany) were used. The electrophysiological reactions of sex pheromones and major volatile components of the conifers were confirmed using 5 males and females each.

A graph of the male electrophysiological response to the treatment amount of sex pheromone (3Z, 6Z, 9Z, 12Z, 15Z)-henicosapentaene is shown in FIG. 8 .

As shown in FIG. 8 , male star moths (3Z,6Z,9Z,12Z,15Z)- Henicosapentaene at 30 μg treatment (ab) and (c) 1 μg to 5 μg There was a statistically significant difference until treatment (c or bc). There was no statistically significant difference in response to each treatment dose when treated with more than 30 μg (a or ab) (Duncan's test, F _(9,60) = 3.24, p = 0.0029). Numerical values including the same letter in FIG. 8 mean that there is no statistical difference.

Example 4. Outdoor Attraction Test

After processing 0.1 mg to 3 mg of artificially synthesized sex pheromone (3Z, 6Z, 9Z, 12Z, 15Z)-henicosapentaene in Sleeve stopper septa (bottom ID × OD 2.4 mm × 5.3 mm), An outdoor attraction experiment was conducted using a delta trap (FIG. 9). (3Z, 6Z, 9Z, 12Z, 15Z)-Henicosapentaene treatment amount according to the male star moth attraction test graph is shown in Figure 10.

As shown in FIG. 10 , as the treatment amount of pheromone was increased, the number of male star moths attracted also increased, and the average number of catches for each treatment amount showed a statistically significant difference (randomized block design anova, duncan's test, F _{( 7,12)} = 74.51, p < 0.0001). Numerical values including the same letter in FIG. 10 mean that there is no statistical difference. The mean populations of male caterpillars collected at treatment doses of 0.1, 1, 2, and 3 mg were 27.0 (d), 127.3 (c), 148.5 (b), and 177.5 (a), respectively, and the mean of the untreated control group The number of catches was 0.3 (e).

In order to search for more effective traps in lure of the caterpillar moth, the attraction force between the delta-trap and the bucket-trap was compared. 1 mg of (3Z,6Z,9Z,12Z,15Z)-henicosapentaene was treated with a lure. Fig. 11 shows the catching ability of the caterpillar moth according to the pheromone trap type.

As shown in FIG. 11 , an average of 8.0 individuals of a bucket trap and an average of 118.6 individuals of a delta trap were collected, confirming that the trapping ability of the delta trap was superior to that of the bucket trap.

Claims (15)

A composition for controlling moths comprising henicosapentaene. The composition of claim 1, wherein the henicosapentaene is (3Z,6Z,9Z,12Z,15Z)-henicosapentaene. The composition of claim 1, wherein the henicosapentaene is a sex pheromone. The method according to claim 1, wherein the moth is a larvae moth ( Naxa seriaria ) The composition. The composition of claim 1, wherein the composition attracts or traps moths. The composition of claim 1 , wherein the composition attracts or captures male moths. The method according to claim 1, wherein the formulation is selected from the group consisting of rubber septum, sachet, capsule, gel, emulsion, suspension, emulsion, paste, cream, oil, powder, wax, and spray. composition. A first step of producing icosapentaen-1-ol from Ethyl-icosapentaenoate;
a second step of producing icosapetaene-1-yl 4-methylbenzenesulfonate from icosapentaen-1-ol; and
a third step of producing henicosapentaene from icosapentaen-1-yl 4-methylbenzenesulfonate;
A method for preparing a composition comprising henicosapentaene. The method according to claim 8, wherein the first step is carried out in the presence of any one or more of lithium aluminum hydride (LAH) and tetrahydrofuran (THF). The method of claim 8, wherein the second step is performed in the presence of at least one of para-toluenesulfonyl chloride (TsCl) and pyridine. The method of claim 8, wherein the third step is performed in the presence of at least one _{of methyl magnesium bromide (CH 3} BrMg) and a dilithium tetrachlorocuprate (II) solution (Li ₂ CuCl _{4 ).} A trap for controlling moths containing henicosapentaene. The trap of claim 12 , wherein the trap is a delta-trap or a bucket-trap. A method for controlling moths, comprising the step of dripping, leaving, spraying, applying, or a combination thereof of a composition comprising henicosapentaene. A method for monitoring a moth, comprising the step of leaving, spraying, applying a composition comprising henicosapentaene, or performing a combination thereof.

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