A yponomeuta plumbella sex pheromone antagonist and application thereof

Abstract

This invention discloses a sex pheromone antagonist for the poplar leafminer moth and its application. The active ingredient of the sex pheromone antagonist is cis-13-octadecene-15-ynyl alcohol. The sex pheromone antagonist of this invention can interfere with the orientation of male poplar leafminer moths towards females, causing males to become disoriented, thereby reducing the probability of encounters between males and females, interfering with mating, reducing the reproductive rate, and gradually controlling the extinction of the pest population, thus achieving the purpose of pest control. This invention can significantly reduce the damage caused by the poplar leafminer moth and is also environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of pest control technology, and more specifically, to a sex pheromone antagonist of the poplar moth and its application. Background Technology

[0002] Insect sex pheromones are trace chemical substances secreted by special secretory organs of a particular sex of the same insect species. They can be received by receptors of opposite sexes of the same species and cause certain behavioral responses or physiological effects (such as courtship, directional mating, and mating) in the opposite sexes.

[0003] Moth sex pheromones typically consist of a primary component and a secondary component. The primary component stimulates male moths to exhibit "long-distance" chemotaxis, attracting them, while the secondary component induces "short-distance" localization behavior, causing male moths to descend, approach, crawl, and mate. Studies have found that secondary components of sex pheromones can act as pheromone enhancers, increasing the trapping effect of the primary component, or as antagonists, participating in the regulation of moth mating behavior alongside the primary component. For example, the secondary component Z11-16:OH in the gonads of female cotton bollworms acts as an antagonist, participating in the regulation of optimal mating time in cotton bollworms along with the primary sex pheromone component, providing a new approach for developing pest repellents and mating disruptors based on sex pheromone antagonists.

[0004] The courtship and mating behavior of the poplar leafminer moth is closely related to sex pheromones. Cis-13,trans-15-octadecadienal is the main sex pheromone component of the poplar leafminer moth, attracting male adults. During their research on the mating behavior of the poplar leafminer moth, the inventors' team discovered that male moths exhibit multiple matings, while female moths do not choose other males for secondary mating after initial mating. We hypothesize that other sex pheromone components may exist in the gonads of female poplar leafminer moths to repel males, thus preventing multiple matings. Therefore, identifying active ingredients that inhibit multiple mating behavior in female poplar leafminer moths, and subsequently developing sex pheromone antagonists for the poplar leafminer moth, has significant research and application value. Summary of the Invention

[0005] This invention provides a sex pheromone antagonist for the poplar moth, wherein the active ingredient of the sex pheromone antagonist is cis-13-octadecene-15-ynyl alcohol, the structural formula of which is shown in Formula I.

[0006]

[0007] The preparation method of the cis-13-octadecene-15-kynyl alcohol includes the following steps:

[0008] (1) 1-Bromo-2-pentyne reacts with triphenylphosphine to generate pento-2-ynyltriphenylphosphine bromide;

[0009] (2) Pentyl-2-ynyltriphenylphosphine bromide was reacted with 13-hydroxy-1-tetridealdehyde to prepare cis-13-octadecene-15-ynyl alcohol.

[0010] Specifically, the preparation method of the cis-13-octadecene-15-kynyl alcohol further includes one or more of the following (1)-(5):

[0011] (1) Under N2 protection, 1-bromo-2-pentyne and triphenylphosphine were dissolved in anhydrous acetonitrile and reacted at 100°C for 48 h to generate penty-2-ynyltriphenylphosphine bromide.

[0012] (2) The molar ratio of 1-bromo-2-pentyne to triphenylphosphine is 5:6;

[0013] (3) The molar ratio of pentyl-2-ynyltriphenylphosphine bromide to 13-hydroxy-1-tridecylaldehyde is 10:9;

[0014] (4) Add 100 ml of anhydrous THF to pentyl-2-ynyltriphenylphosphine bromide to dissolve it, then cool the solution to -78°C, add NaHDMS dropwise, stir for 30 min, add 13-hydroxy-1-tetrazol dropwise, continue the reaction for 2 h, add water to terminate the reaction, then extract the reaction solution with ethyl acetate, wash the ethyl acetate extract with water, dry it, and evaporate the solvent to obtain the crude product of cis-13-octadecene-15-ynyl alcohol;

[0015] (5) The 13-hydroxy-1-tridecane is prepared by the following method: under N2 protection, 1,13-tridecanediol and PCC (pyridine chlorochromate) are dissolved in anhydrous CH2Cl2 and reacted at room temperature for 3 h to obtain 13-hydroxy-1-tridecane, wherein the molar ratio of 1,13-tridecanediol to PCC (pyridine chlorochromate) is 1:1.02.

[0016] The present invention also provides the application of the aforementioned sex pheromone antagonist in the control of poplar leafminer moth.

[0017] Specifically, the method of using the sex pheromone antagonist is as follows: adding the cis-13-octadecene-15-ynyl alcohol to a carrier and releasing it into the environment through the carrier.

[0018] The carrier is any one of plastic capillary tube, butyl rubber stopper, natural rubber stopper, plastic slow-release bag or slow-release tablet.

[0019] The dosage of the sex pheromone antagonist is 5 mg / site, the number of hanging in the forest is 160-200 sites / acre, and the setting height is 1.5-3m above the ground.

[0020] The beneficial effects of this invention include:

[0021] The cis-13-octadecene-15-ynyl alcohol provided by this invention, as a sex pheromone antagonist, can interfere with the positioning of male poplar moths on females, causing males to become disoriented, thereby reducing the probability of male and female insects meeting, interfering with mating, reducing the reproduction rate, and gradually controlling the extinction of the pest population, thus achieving the purpose of prevention and control.

[0022] The sex pheromone antagonist of this invention provides a new approach for the development of mating interference agents for pests. It has important application and economic value in the pollution-free control of poplar moth, and also has significant social and ecological benefits. Attached Figure Description

[0023] Figure 1 EAD response spectrum of male insects to extracts from the gonads of the poplar moth;

[0024] Figure 2 EAD reaction spectra of male insects with cis-13, trans-15-octadecadienal and cis-13-octadecen-15-ynyl alcohol;

[0025] Figure 3 The synthetic route for cis-13-octadecene-15-alkynol;

[0026] Figure 4 This document shows the trapping of *Populus tomentosa* moths in non-maze and maze areas of Suiping County, Henan Province in 2022. Detailed Implementation

[0027] The present invention will be further described and illustrated below with reference to embodiments. However, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the present invention and the embodiments, all other inventions and embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0029] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0030] Example 1: Component Analysis of the Gonadal Extract of *Populus simonii*

[0031] (1) Extraction of gonadal extract

[0032] Sampling by solvent extraction: After mating, female adult poplar moths were treated in the dark for 4 hours. Their gonads were then removed with pointed forceps. Three gonads were placed in a 1ml glass bottle, and 50ul of n-hexane was added for extraction for 40 minutes. The hexane extract was then concentrated to 1ul and sealed in a capillary glass tube for storage at -20℃. The treatment was repeated 10 times.

[0033] (2) GC-EAD analysis of gonadal extracts from male adult moths of the Yangxiaozhou moth

[0034] The gonadal extract of *Polygonum hydropiper* was analyzed by gas chromatography-electroangiography (GC-EAD), and the corresponding GC-EAD chromatograms were obtained. The conditions were: Agilent 7890A GC-EAD system (USA) - Syntech GC-EAD system (Netherlands); DB-5MS column (30m × 0.25mm × 0.25μm); high-purity nitrogen as carrier gas; flow rate of 1ml / min; splitless injection; split valve opened after 1min; injection volume of 1µl; injection port temperature of 250℃; temperature program: initial temperature 60℃, hold for 2min, increase to 280℃ at 8℃ / min, hold for 20min. EAG probe: PRG-2, forked antennal retainer; IDAC converter: Auto Spike, IDAC2 / 3, Syntech; amplifier: UN-06, Syntech. Two to three days after emergence, the antennae of male Populus tomentosa moths were cut off from the base with dissecting scissors, and about 0.5 mm of the tip of the antennae were removed. The antennae were then connected to the two silver electrodes of the forked antennae holder of the EAG probe (PRG-2) with conductive glue.

[0035] Through spectral analysis ( Figure 1 The gonadal extract contained components that caused significant electrophysiological responses in the antennae of male Populus tomentosa moths, with retention times of 20.66 min and 23.02 min, respectively.

[0036] (3) GC-MS identification of compound components

[0037] Gonadal extracts were analyzed by gas chromatography-mass spectrometry (GC-MS) using an Agilent 7890B-5977 column (DB-5MS).

[0038] (30m×0.25mm×0.25μm), carrier gas is high-purity helium, flow rate is 1ml / min, splitless injection, split valve opens after 1min. Injection volume is 1ul, injection port temperature is 250℃, and the temperature program is the same as the temperature method in step (2). MS analysis conditions: EI ion source, electron energy 70ev, transfer line temperature 250℃, ion source temperature 220℃, scan range 41-650amu. By comparing with the standard spectrum in the Nist02 spectral library, the structure given by the component with a retention time of 20.66min is cis-13,trans-15-octadecadienal (molecular weight m / z: 264), and the structure given by the component with a retention time of 23.02min is cis-13-octadecene-15-alkynol (molecular weight m / z: 264).

[0039] (4) Changes in sex pheromone content before and after mating

[0040] Sampling by solvent extraction: Unmated and mated female adult moths of the poplar leafminer were treated in the dark for 4 hours. The gonads were then removed with pointed tweezers, and three gonads were placed in a 1 ml glass bottle. 50 μL of n-hexane was added and extracted for 40 min. The hexane extract was concentrated to 1 μL and sealed in a capillary glass tube for storage at -20℃. The treatment was repeated 10 times. The content was determined using octadecane (10 ng / μL) as an internal standard. Gas chromatography analysis was performed under the same conditions as in step (2), and the results are shown in Table 1.

[0041] Table 1. Changes in the contents of cis-13, trans-15-octadecadienal and cis-13-octadecene-15-ynyl alcohol in the gonad extracts of female *Populus simonii* moths after different treatments

[0042] deal with cis-13,trans-15-octadecadienal (ng) cis-13-octadecene-15-kynyl alcohol (ng) Unmated 8.5±0.23ng 0.59±0.43ng After mating 4.4±0.74ng* 3.19±0.39ng***

[0043] The data in Table 1 show that after mating, the content of cis-13,trans-15-octadecadienal in the glands of female Populus tomentosa moths decreased significantly, while the content of cis-13-octadecadien-15-alkynol increased significantly.

[0044] (5) Synthesis of cis-13-octadecene-15-kynyl alcohol

[0045] according to Figure 3 The preparation is carried out according to the synthetic route described above, and the specific steps are as follows:

[0046] 10.97 g of PCC (pyridine chlorochromate, 0.051 mol) was added to 100 mL of anhydrous CH₂Cl₂. Under N₂ protection, 10.80 g of 1,13-tridecanediol (0.05 mol) was rapidly added with constant stirring. The reaction was carried out at room temperature for 3 h. Then, 20 mL of water and 100 mL of diethyl ether were added and stirred. The mixture was then filtered through silica gel. The filtrate was extracted three times using a separatory funnel. The organic phase was washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was evaporated. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (2 / 1) as the eluent to give 7.28 g of 13-hydroxy-1-tridecanedialdehyde (68% yield, 96% purity). NMR data: 1 ¹H-NMR (500MHz, CDCl₃) δ 1.26 (6H, m), 1.30 (6H, m), 1.33 (2H, m), 1.43 (2H, m), 1.58 (4H, m), 2.38 (2H, m), 3.62 (2H, m), 9.72 (1H, t, J = 2.0 Hz). Mass spectrometry data: GC-MS (70 eV, EI): 214.

[0047] Under N2 protection, 2.94 g of 1-bromo-2-pentyne (0.02 mol) and 6.29 g of triphenylphosphine (PPh3 0.024 mol) were dissolved in 30 mL of anhydrous acetonitrile (CH3CN), and the reaction was carried out at 100 °C for 48 h. After evaporation of the solvent, crude pentyryl-2-ynyltriphenylphosphine bromide was obtained. This crude product was then dissolved in 100 mL of anhydrous THF (tetrahydrofuran), and the solution was cooled to -78 °C. 20 mL of NaHDMS (hexamethyldisilamide sodium, 0.02 mol, 1 M) was added dropwise, and the mixture was stirred for 30 min. Then, 3.85 g of 13-hydroxy-1-tetrazaldehyde (0.018 mol) was added dropwise, and the reaction was continued for 2 h. The reaction was terminated by adding water, and the reaction mixture was extracted three times with 10 mL of ethyl acetate each time. The ethyl acetate extracts were combined, washed with water, and dried over anhydrous sodium sulfate. The solution was evaporated using a rotary evaporator to obtain crude cis-13-octadecene-15-kynyl alcohol, which was then purified by silica gel column chromatography using petroleum ether / ethyl acetate as eluent (10 / 1) to give 3.63 g of cis-13-octadecene-15-kynyl alcohol (yield 62%, purity 95%). NMR data: 1 ¹H-NMR (500MHz, CDCl₃) δ 1.00 (3H, t, J = 7.5Hz), 1.28–1.38 (¹⁸H, m), 1.60–1.66 (2H, m), 2.15–2.44 (4H, m), 3.62 (2H, m), 5.42–5.47 (¹H, m), 6.19–6.28 (¹H, m). Mass spectrometry data: GC-MS (70eV, EI): 264.

[0048] (6) GC-EAD analysis of male adult moths of the poppy leafminer on pheromone standards

[0049] A 30 ng / µl solution of cis-13,trans-15-octadecadienal (preparation method see CN110372482A) and cis-13-octadecene-15-ynyl alcohol was prepared in n-hexane. The analytical conditions were the same as in (2), with an injection volume of 1 µl. The EAD reaction chromatograms of male insects with cis-13,trans-15-octadecadienal and cis-13-octadecene-15-ynyl alcohol are shown below. Figure 2 As shown in the figure, the compounds cis-13, trans-15-octadecadienal and cis-13-octadecen-15-kynyl alcohol can all induce significant electrophysiological responses in the antennae.

[0050] Example 2: Effects of cis-13,trans-15-octadecadienal and cis-13-octadecen-15-kynyl alcohol on the mating behavior of the poplar moth.

[0051] Test methods

[0052] Hexane solutions of cis-13,trans-15-octadecadienal with concentrations of 0.1 ng / ul, 1 ng / ul, and 10 ng / ul were prepared as cis-13,trans-15-octadecadienal volatiles; hexane solutions of cis-13-octadecene-15-ynyl alcohol with concentrations of 0.1 ng / ul, 1 ng / ul, and 10 ng / ul were prepared as cis-13-octadecene-15-ynyl alcohol volatiles.

[0053] The study was divided into three groups: n-hexane (A), cis-13,trans-15-octadecadienal volatiles (B), and cis-13-octadecene-15-ynyl alcohol volatiles (C), with 10 replicates per group. 1 μL of the volatiles or n-hexane solution was applied to the tail of female *S. chinensis* moths. After the n-hexane evaporated, the female moths were placed in test tubes sealed with cotton (2 cm in diameter, 10 cm in length, with the cotton slightly moistened with honey), along with one newly emerged male *S. chinensis* moth. The test tubes were placed in an incubator with a light-dark ratio of 16L:8D, a temperature of 26±2℃, and a humidity of approximately 70%. Observation lasted for 11 hours, from two hours before the dark period to one hour after the dark period. Observations were made every half hour using a weak red light. Mating between males and females was recorded, and the mating rate (mating rate = actual mated number / number of matable moths × 100%) was calculated. The results are shown in Table 2.

[0054] Table 2. Effects of different treatments on the mating rate of *Symplocos pubescens*

[0055]

[0056]

[0057] As shown in Table 2, the sex pheromone component cis-13,trans-15-octadecadienal can increase the mating rate between male and female *Populus simonii*. In the test experiments ranging from 0.1 ng to 10 ng, the mating rate increased with increasing concentration. Conversely, cis-13-octadecadien-15-ynyl alcohol can significantly inhibit mating behavior between male and female. In the test experiments ranging from 0.1 ng to 10 ng, the mating rate decreased significantly with increasing concentration. Example 3: Inhibition test of cis-13-octadecadien-15-ynyl alcohol on the attraction of *Populus simonii* to lures.

[0058] From April 15 to May 20, 2022, a comparative experiment was conducted in a poplar forest in Fugou, Henan Province, to trap poplar moths using sex pheromone lures and lures with added sex pheromone antagonists.

[0059] 1. Material preparation:

[0060] (1) Preparation of sex pheromone lure for the Yang Xiaozhou moth: 5 mg of cis-13,trans-15-octadecadienal was added to a polyethylene plastic tube (purchased from the market) to prepare the sex pheromone lure for the Yang Xiaozhou moth.

[0061] (2) Preparation of mixed lures for the sex pheromone attractant and antagonist of the poppy moth: 0.25 mg, 2.5 mg and 5 mg of cis-13-octadecene-15-ynyl alcohol were added to the sex pheromone lures of the poppy moth, respectively, to prepare mixed lures for the sex pheromone attractant and antagonist of the poppy moth. The treatments were named A1, A2 and A3 respectively according to the dosage of cis-13-octadecene-15-ynyl alcohol added from low to high.

[0062] (3) The trap is a barrel-shaped trap (purchased from the market).

[0063] 2. Experimental Design:

[0064] (1) Four types of traps were made by fixing one sex pheromone lure (CK) of the small moth and one lure mixed with different doses of attractant and antagonist inside a barrel-shaped trap, which served as four experimental treatments.

[0065] (2) The test site was Fugou, Henan Province. Four types of traps were set up in the forest, i.e., four experimental treatments. Each experimental treatment had three replicates. The distance between the traps in the group was about 50 meters. The traps were fixed between two trees and 1.5 meters above the ground.

[0066] (3) Data survey: The investigators recorded the number of male adults trapped every 4 days and removed the trapped male adults. The results are shown in Table 3.

[0067] Table 3. Results of the experiment on sex pheromone antagonists of Populus tomentosa in Fugou County, Henan Province

[0068] Core category Average daily catch per trap / heads Total number of animals trapped / heads CK 2.44±0.72c 263 A1 0.75±0.23b 81 A2 0.14±0.07a 15 A3 0.074±0.02a 8

[0069] The experimental results showed that the sex pheromone antagonist cis-13-octadecene-15-ynyl alcohol inhibited the attraction of male adult poplar moths, and the inhibition was observed at different doses; the inhibitory effect was strengthened with the increase of the dosage.

[0070] Example 4: Inhibition test of cis-13-octadecene-15-ynyl alcohol on the attraction of poplar leafminer moths by lures in different regions.

[0071] From June 1st to June 20th, 2022, a comparative experiment was conducted in a poplar forest in Dengzhou, Henan Province, to trap the poplar moth using sex pheromone lures and lures containing sex pheromone antagonists. The experimental materials and design were the same as in Example 3, and the results are shown in Table 4.

[0072] Table 4. Results of the experiment on sex pheromone antagonists for the poppy moth in Dengzhou, Henan Province.

[0073]

[0074]

[0075] The experimental results also showed that the sex pheromone antagonist cis-13-octadecene-15-ynyl alcohol inhibited the attraction of male adult poplar moths, and the inhibition was observed at different doses; the inhibitory effect was strengthened with the increase of the dosage.

[0076] Example 5: Poplar Small Boat Moth Adult Descent Experiment

[0077] The mating method for pest control involves releasing large amounts of sex pheromones within a defined area, keeping the antennae of male adults constantly exposed to high concentrations of sex pheromones, or releasing large amounts of pheromone-related homologues, inhibitors, or antagonists to interfere with normal chemical communication between male and female adults. This prevents them from locating females for mating, thereby controlling their mating and reproduction. The mating effect is judged by the effectiveness of sex pheromone lures in capturing target pests. If fewer pests are captured in the mating zone than in the non-mating zone, a mating effect exists, indicating a reduced or absent attraction of female adults. Since sex pheromone antagonists also reduce the sensitivity of target pests to sex pheromones, their application in mating control can be considered.

[0078] From July 20 to August 9, 2022, a disorientation experiment on the poplar moth was conducted in Fugou, Henan Province.

[0079] 1. Material preparation:

[0080] (1) The preparation of the sex pheromone lure of the Yang Xiaozhou moth is the same as that in Example 3.

[0081] (2) Preparation of antagonist for poplar moth: 5 mg of cis-13-octadecene-15-ethynol was added to polyethylene plastic tubes to prepare the antagonist for poplar moth sex pheromone.

[0082] (3) The trap is a barrel-shaped trap (purchased from the market).

[0083] 2. Experimental Design:

[0084] (1) A sex pheromone lure for the moth *Pterocarya stenoptera* is made by fixing one sex pheromone lure core inside a barrel-shaped trap.

[0085] (2) Select an 8-mu (approximately 0.33 hectares) poplar forest as the maze area (Group A). ​​1600 poplar leafminer sex pheromone antagonists were directly fixed to the poplar trees, with each antagonist spaced 5 meters apart and 1.5 meters above the ground. At the same time, 5 poplar leafminer sex pheromone traps were set up in the maze area, with a spacing of approximately 50 meters between the traps. The traps were fixed between two trees and 1.5 meters above the ground.

[0086] An 8-acre poplar grove was selected as the blank control group (CK group), with no treatment. Five poplar moth sex pheromone traps were set up in the blank control group area, with a spacing of about 50 meters between the traps. The traps were fixed between two trees and 1.5 meters off the ground.

[0087] (3) Data survey: The investigators recorded the number of male adults trapped every 4 days and removed the trapped male adults. The results are shown in Table 5.

[0088] Table 5. Comparison of the number of *Populus albopictus* moths trapped in non-misty areas and misty areas in Fugou County, Henan Province in 2022.

[0089] date CK trapping quantity / head A Trapping quantity / head A. Processing disorientation rate (%) 7.24 89 50 43.8 7.28 78 30 61.5 8.1 60 29 51.7 8.5 102 22 78.4 8.9 84 10 88.1

[0090] Experiments have shown that placing a sex pheromone antagonist, cis-13-octadecene-15-ynyl alcohol, in forest areas infested by the poplar moth has a certain disorientation effect on male adult poplar moths.

[0091] Example 6: Experiment on the mating behavior of adult Poplar moths in different regions using cis-13-octadecene-15-kynyl alcohol.

[0092] From May 1st to 20th, 2023, a disorientation experiment on the poplar moth was conducted in Suiping, Henan Province, using cis-13-octadecene-15-alkynol.

[0093] 1. Material preparation: Same as in Example 5.

[0094] 2. Experimental Design:

[0095] (1) The preparation method of the Yang Xiaozhou moth sex pheromone trap is the same as in Example 5.

[0096] (2) Select a 3-mu (approximately 0.5 acres) poplar grove as the maze area and directly fix 480 poplar leafminer sex pheromone antagonists on the poplar trees, with each antagonist spaced 5 meters apart and 1.5 meters above the ground. At the same time, set up 3 poplar leafminer sex pheromone traps in the maze area, with the traps spaced approximately 50 meters apart and fixed between two trees, 1.5 meters above the ground.

[0097] A 3-acre poplar grove was selected as a blank control group, with no treatment performed. Three poplar moth sex pheromone traps were set up in the blank control group area, with a spacing of approximately 50 meters between the traps. The traps were fixed between two trees and 1.5 meters off the ground.

[0098] (3) Data collection: Investigators recorded the number of male adults trapped every 4 days and removed the trapped male adults. The results are shown in […]. Figure 4 See Table 6.

[0099] Table 6. Comparison of the number of Populus tomentosa moths trapped in non-maze zones and maze zones in Suiping County, Henan Province in 2023.

[0100]

[0101]

[0102] The experiment also showed that placing a sex pheromone antagonist, cis-13-octadecene-15-ynyl alcohol, in forest areas infested by the poplar moth had a certain disorientation effect on male adult poplar moths.

[0103] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A gypsy moth sex pheromone antagonist, characterized in that, The active ingredient of the sex pheromone antagonist is cis-13-octadecene-15-ynyl alcohol, whose structural formula is shown in Formula I.

2. The gypsy moth sex pheromone antagonist of claim 1, wherein The preparation method of the cis-13-octadecene-15-kynyl alcohol includes the following steps: (1) 1-Bromo-2-pentyne reacts with triphenylphosphine to generate pento-2-ynyltriphenylphosphine bromide; (2) Pentyl-2-ynyltriphenylphosphine bromide was reacted with 13-hydroxy-1-tetrazol to prepare cis-13-octadecene-15-ynyl alcohol.

3. The gypsy moth sex pheromone antagonist of claim 2, wherein The method for preparing cis-13-octadecene-15-kynyl alcohol further includes one or more of the following (1)-(5): (1) Under N2 protection, 1-bromo-2-pentyne and triphenylphosphine were dissolved in anhydrous acetonitrile and reacted at 100°C for 48 h to generate penty-2-ynyltriphenylphosphine bromide. (2) The molar ratio of 1-bromo-2-pentyne to triphenylphosphine is 5:6; (3) The molar ratio of pentyl-2-ynyltriphenylphosphine bromide to 13-hydroxy-1-tridecylaldehyde is 10:9; (4) Add 100 ml of anhydrous THF to pentyl-2-ynyltriphenylphosphine bromide to dissolve it, then cool the solution to -78°C, add NaHDMS dropwise, stir for 30 min, add 13-hydroxy-1-tetrazol dropwise, continue the reaction for 2 h, add water to terminate the reaction, then extract the reaction solution with ethyl acetate, wash the ethyl acetate extract with water, dry it, and evaporate the solvent to obtain the crude product of cis-13-octadecene-15-ynyl alcohol; (5) The 13-hydroxy-1-tridecaldehyde was prepared by the following method: Under N2 protection, 1,13-tridecanediol and PCC are dissolved in anhydrous CH2Cl2 and reacted at room temperature for 3 hours to prepare 13-hydroxy-1-tridecanediol, wherein the molar ratio of 1,13-tridecanediol to PCC is 1:1.

02.

4. The application of the sex pheromone antagonist according to any one of claims 1-3 in the control of poplar leafminer moth.

5. Use according to claim 4, characterized in that, The method of using the sex pheromone antagonist is as follows: add the cis-13-octadecene-15-ynyl alcohol to a carrier and release it into the environment through the carrier.

6. Use according to claim 5, characterized in that, The carrier is any one of plastic capillary tube, butyl rubber stopper, natural rubber stopper, plastic slow-release bag or slow-release tablet.

7. Use according to claim 4, characterized in that, The dosage of the sex pheromone antagonist is 5 mg / site, the number of hanging in the forest is 160-200 sites / acre, and the setting height is 1.5-3m above the ground.

Images