KR100613900B1 - Sex pheromone of Aphidoletes aphidimyza that can be used to monitor the population of aphids and synthetic method thereof - Google Patents

Abstract

The present invention relates to an aphid-fly fly pheromone and a method for synthesizing the aphid-fly fly used for the density investigation of the aphid fly in aphids biological control using aphid fly, the aphid fly fly pheromone of the present invention Prediction of the density in the package before or after spinning allows for efficient control of aphids.

Aphids * Aphids flies * Sex pheromones * Synthesis * Biological control

Description

Sex pheromone of Aphidoletes aphidimyza that can be used to monitor the population of aphids and synthetic method according to aphids.

FIG. 1 shows a flame ionization detector (FID) and an electrotactile graph detector (EAD) response to candy date pheromone (CP) extracted from a female aphid fly.
Figure 2 shows the results of assaying the attracting effect of males with Y-tubes using aphid-fly fly females and four structural isomers.
Figure 3a shows the results of investigating the number of aphid flies attracted to the trap of each of the four structural isomers of (2,7) -diacetoxytridecane,
Figure 3b shows the results of investigating the number of aphid flies attracted to each trap when (2R, 7S) -diacetoxytridecane mixed with other structural isomers.

The present invention relates to aphids fly pheromone used in the density control of the aphids fly, and the method for synthesizing the biological control of aphids using aphids fly. Aphid fly pheromone of the present invention enables efficient control of aphids by predicting the density in the package before or after radiating aphid fly.

Aphids are belonging to the genus Amphitaceae, Hampari, and are known to be distributed in Europe, Asia, North America and Africa. Aphids fly flies up to 80 species of aphids and do not fly far from the radiation point, so they are widely used for biological control of aphids.

In addition, adult aphid flies are active at night, so they adapt well to high temperatures even during high temperatures during the day in the greenhouse, so they are suitable for the environment of our country. Can also be used as.

The development period of aphid hogs is very short, so one generation can be completed in 15 days at 25 ℃. Aphid fly fertility is determined by the proportion of females in the population (60–70%) and the ability of the females to spawn aphids. Eggs spawn directly near the aphid colony, and only three eggs per cucumber leaf spawn. The spawning water depends on the aphid density and the mortality of the larvae is low after hatching.

The larvae suck on the aphid's hemo-lymph and sometimes eat all the aphid colonies. Larvae secrete special toxins, especially if the aphids are dense, paralyzing aphids twice as much and then eating.

Aphid hogs have already been commercialized in Europe and North America, and are now sold by 34 natural enemies in North America as of 1994 and by four natural companies in Europe as of 1997.

Biological control has the advantages of being safer and environmentally friendly than pharmaceutical control. However, in the case of aphid fly flies, aphids are provided to feed aphids so that the cost of production is higher than other biological controls. It is a disadvantage.

Therefore, it is very important to accurately and quickly determine the density of the aphid fly before or after the release of the aphid fly in order to perform the biological control work using the aphid fly as economically and effectively.

Accordingly, the present inventors have found that the aphid fly can be used efficiently and economically by predicting the density in the package before and after emitting the aphid fly using artificially synthesized aphids. .

Accordingly, it is an object of the present invention to provide aphids fly pheromone used for predicting the density in the packaging of aphids fly in the biological control of aphids using aphids.

It is also an object of the present invention to provide a method for synthesizing the aphids fly pheromone.

The present invention relates to aphids fly pheromone used in the density control of the aphids fly, and the method for synthesizing the biological control of aphids using aphids fly. Aphid fly pheromone of the present invention enables efficient control of aphids by predicting the density and timing in the package before or after emitting the aphid fly.

The aphid-flying pheromone of the present invention is secreted by females of the natural aphid-flying aphids of aphids, in the present invention by artificially extracting the sex pheromone of the aphids fly, using GC-EAD, GC-MS, NMR, etc. The component was analyzed. The results, aphids hoc Paris sex pheromone is (2R, 7S) - diacetoxy tridecane were found to be ((2 R, 7 S) -DIACETOXYTRIDECANE), to an artificially synthesized in a lump by the present invention aphids of formula Experiments confirmed that the paris pheromone has a male attracting effect.

REFERENCE EXAMPLE 1 Analysis of Components of Aphids' Flies Pheromones

In order to extract the aphid-fly fly pheromone, the pheromone gland between 8 and 9 nodes of the aphid-fly fly female abdomen was separated and extracted with a nucleic acid solvent. Then, the extract was analyzed using gas chromatography (Gs Chromatography), GC-EAD technique that is an analysis method using the antenna of gas chromatography and aphid hog flies as a biosensor. FIG. 1 is a graph showing a flame ionization detector (FID) and an electroantennographic detector (EAD) reaction against candy date pheromone (CP) extracted from one female.

As a result of the analysis, the chemical structure of the aphid-fly fly pheromone was estimated based on the retention index (RI) obtained from three different columns (DB-5, DB-23, and DB-210). It was confirmed that a kind of carbohydrate of 13 carbon atoms having two acetyl groups is a pheromone component of the aphid fly.

Reference Example 2 Synthesis of (2,7) -Diacetoxytridecane ((2,7) -Diacetoxytridecane) as a Model Pheromone Component

Based on the results analyzed in Reference Example 1, a model pheromone component was synthesized according to the following synthesis process, and the synthesis process is shown in Scheme 1 below.

(1) 15 mmol (1.65 ml) of 1,4-dichlorobutane (1,4-Dichlorobutane) and 1.1 g of Mg (45 mmol) were reacted with 50 ml of THF for 3 hours to obtain a Grignard reagent. Forming);

(2) After cooling the reaction solution to 0 ° C, stir 30 ml of THF in a dropwise mixture of 1.12 ml (20 mmol) of acetaldehyde and 2.80 ml (20 mmol) of heptanal. After 30 minutes of reaction, the reaction was terminated with concentrated NH ₄ Cl solution. The reaction product was extracted with ether (3 × 75 ml) and washed with brine, followed by anhydrous magnesium sulfate (MgSO ₄ Drying under reduced pressure;

(3) The reaction product (diols 1, 2, 3 = 1.1: 2: 0.9) of Scheme 1 was prepared using 50 g of silica column in hexane / ether (ether ratio: 15). % To 50%), followed by acetylation of 0.40 g (1.73 mmol) of diol 2 with excess acetic anhydride (1 ml) and pyridine (3 ml) to 0.415 g of diacetoxytridecane by column chromatography. (diacetoxytridecane) (Formula 4 of Scheme 1) (1.38 mmol, 80% yield) was obtained.

EXAMPLES structural isomers (2 R, 7 S) - Synthesis of diacetoxy-tridecane ((2 R, 7 S) -diacetoxytridecanes)

According to the following synthesis process, a sex pheromone of aphids flies was synthesized, and the synthesis process is shown in Scheme 2 below.

(1) 28.6 mmol (2 ml) of (R) -propylene oxide (Formula 5 in Scheme 2) and 40 mmol of 1-penten-5-yl magnesium bromide (1-pentene-5-yl reacting magnesium bromide (Formula 6 in Scheme 2) with 4 mmol (0.76 g) of copper iodide (CuI) as a catalyst at -20 ° C. for 1 hour;

(2) The reaction product was brought to 0 ° C., and then concentrated ammonium chloride (NH ₄ Cl) was added to stop the reaction, and gas chromatography was carried out using (2R) -7-octen-2-ol ((2R) -7-octen-2-ol) (Formula 7 of Scheme 2) pure separation;

(3) oxidation with excess m-chloro-perbenzoic acid (9.6 g, 43 mmol) and dichloromethane for 5 hours at 0 ° C. and 2 hours at room temperature;

(4) treatment with salt (2N NaOH) to extract 3.6 g of terminal epoxide (Formula 8 of Scheme 2) with 50 ml of ether;

(5) 7.0 mmol (1.00 g) of terminal epoxide was added to Co (II) Salen (manufactured by Jacobsens) catalyst (Formula 9 of Scheme 2) in a 2 ml dry THF for 72 hours. (0.80 equiv. H ₂ O (0.1 ml) consumption);

(6) (2R, 7R) -1,2-epoxy-7-hydroxyoctane ((2R, 7R) -1,2-Epoxy-7-hydroxyoctane) (Formula 10 in Scheme 2) was chromatographed [SiO ₂ 10 g; Solvent ether / hexane (1: 1)];

(7) treatment at −25 ° C. for 1 hour under excess pentylmagnesium bromide (21 mmol) and 2.1 mmol (0.40 g) of copper iodide (CuI) catalyst;

(8) (2R, 7S) -stereoisomer (Formula 12 in Scheme 2) was added 2 ml of acetic anhydride and 5 ml of pyridine at room temperature for 12 hours. Esterification; And

(9) using a chromatography represented by the general formula 1 (2 R, 7 S) - diacetoxy tridecane ((2 R, 7 S) -Diacetoxytridecane) ( formula 13 of Scheme 2) to give the 0.90g.

[Formula 1]

Chemical Structural Properties of (2 R , 7 S ) -diacetoxytridecane: Anal. calcd. for C 17 H 32 O 4: C 67.96; H 10.73. Found: C 68.01; H 10.78. 1 H NMR: CDCl 3, d = 4.80-4.92 (2H, m), 2.03 (3H, s), 2.02 (3H, s), 1.45-1.55 (6H, m), 1.21-1.35 (12H, m), 1.19 ( 3H, d), 0.88 (3H, t); GC-MS [ m / z (relative intensity)]: 41 (19), 43 (100), 55 (20), 67 (37), 81 (24), 95 (84), 97 (37), 111 ( 31), 113 (29), 125 (21), 180 (4), 197 (8).

Test Example 1 Bioassay for Structural Isomers (2,7) -Diacetoxytridecane ((2,7) -diacetoxytridecanes)

Examples of structural isomers each synthesized in the same way as the four kinds of ((2R, 7R) -, (2R, 7S) -, (2 S, 7 R) -, (2 S, 7 S) - diacetoxy tridecane The antenna response of aphid-fly fly males to) was analyzed by GC-EAD method. However, while the aphids hoc Paris female and structural isomers as a Y-tube using the four kinds of results of test for incentives of the male, in the female, as also shown in the bivalent 8 of the male 20 objects attracted, (2 R, 7 S) - There was a high attraction effect than when it is a 12 manned by using the female self-diacetoxy-tridecane-diacetoxy-tridecane it is 18, (2 R, 7R). However, for (2S, 7R)-and (2S, 7S)-, 4 and 5, respectively, showed a low attracting effect. From these results, it was confirmed that (2R, 7S) -diacetoxytridecane has sex pheromone activity of aphids.

Test Example 2 Attracting Effect Test Using Trap in Greenhouse

The male attraction effect by the four types of structural isomers used in Test Example 1 was investigated in a package (greenhouse). For capturing males, a sticky wrap treated with a combination of 2-4 components of 1 μg of each sex pheromone candidate was used. Five aphid flies were released from each trap in the greenhouse, and seven days later, the number of aphid flies attracted to each trap was investigated.

As a result, as shown in Figure 3a, (2 R, 7 S ) - if after treatment a different structural isomers on the other hand showed a high attraction effect on the diacetoxy tridecane treatment showed very little incentive effects similar to the untreated.

Further, (2 R, 7 S) - When it was treated a mixture of different structural isomers material in diacetoxy tridecane, as indicated in Figure 3b, (2 R, 7 R ) - and (2 S, 7 R) In the mixed-treat traps, the number of attracted males was rather low to inhibit attraction.

Therefore, as in the case of Test Example 1, it was found that ( 2R , 7S ) -diacetoxytridecane had an excellent male attraction effect.

As described above, the aphid-fly fly pheromone of the present invention is used for the investigation of the density of the aphid fly in the biological control of aphids using aphids fly, thereby predicting the density in the package before or after radiating aphids fly This enables efficient control of aphids.

Claims (3)

(2R, 7S) -diacetoxytridecane ((2R, 7S) -diacetoxytridecane), which is an aphid-fly fly pheromone compound represented by Formula 1 below. [Formula 1]

A male aphid-fly fly attractant composition containing the aphid-fly fly pheromone compound of Formula 1 as an active ingredient. [Formula 1]

(1) 4 mmol (0.76) of 28.6 mmol (2 ml) of (R) -propylene oxide and 40 mmol of 1-pentene-5-yl magnesium bromide g) copper iodide (CuI) as a catalyst for reaction at −20 ° C. for 1 hour; (2) The reaction product was brought to 0 ° C., and then concentrated ammonium chloride (NH ₄ Cl) was added to stop the reaction, and gas chromatography was carried out using (2R) -7-octen-2-ol ((2R) -7-octen-2-ol) pure separation; (3) oxidation with excess m-chloro-perbenzoic acid (9.6 g, 43 mmol) and dichloromethane for 5 hours at 0 ° C. and 2 hours at room temperature; (4) treatment with salt (2N NaOH) to extract 3.6 g of terminal epoxide with 50 ml of ether; (5) 7.0 mmol (1.00 g) of terminal epoxide was combined with Co (II) salene (salene (manufactured by Jacobsens)) catalyst in HKR (0.80 equivalents of H ₂ O for 72 hours in 2 ml of dry THF. (0.1 ml) consumption); (6) (2R, 7R) -1,2-epoxy-7-hydroxyoctane ((2R, 7R) -1,2-Epoxy-7-hydroxyoctane) was chromatographed [10 g of SiO ₂ ; Solvent ether / hexane (1: 1)]; (7) treatment at −25 ° C. for 1 hour under excess pentylmagnesium bromide (21 mmol) and 2.1 mmol (0.40 g) of copper iodide (CuI) catalyst; (8) adding (2R, 7S) -stereoisomer (2R, 7S) -stereoisomer to 2 ml of acetic anhydride and 5 ml of pyridine for 12 hours at room temperature; And (9) using a chromatography (2 R, 7 S) - diacetoxy tridecane ((2 R, 7 S) -Diacetoxytridecane) 0.90g tablet; Method for synthesizing aphids fly pheromone compound of the formula (1) comprising a. [Formula 1]

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