Cerurin, an attractant for cerura erma, and use thereof

Abstract

The present application relates to the cedar moth sex pheromone, attractant and its application, the sex pheromone component mainly includes anti-9-21 carbon alkene, can attract to cedar moth adult in large quantities, especially with anti-9-21 carbon alkene, anti-7-9-21 carbon diene, 9-8-10-21 carbon diene and anti-6-8-21 carbon diene the sex pheromone attractant trapping effect most outstanding with mass ratio 1:1:0.25:0.25 composition.The sex pheromone and attractant prepared by it can be used for the insect situation of cedar moth forecast and large-scale trapping, and is environment-friendly, safe, has significant ecological benefits and economic benefits.

Description

Technical Field

[0001] This application relates to the field of pest control technology, and more specifically, to the sex pheromone of the teak moth, attractants, and their applications. Background Technology

[0002] The teak camel moth (Hyblaea puera) belongs to the superfamily Hyblaeoidea, family Hyblaeidae, and genus Hyblaea. Native to South and Southeast Asia, it is a major leaf-eating pest of the teak tree (Tectona grandis). After being introduced to Asia, the Americas, and Africa, it spread to over 30 countries and regions. In my country, besides teak, the teak camel moth also feeds on various other plants, including Avicenni, Lamiaceae, and Verbenaceae. This insect possesses strong environmental adaptability, reproductive capacity, and flight ability, allowing it to migrate and cause damage between different planting areas, resulting in sudden and unpredictable population outbreaks. In 2010, the teak camel moth first appeared in Guangxi, my country, damaging the mangrove plant Avicennia marina, and in 2015, a large-scale infestation occurred, almost completely depleting the leaves of the Avicennia marina, leaving only the branches and stems. Teak moth damage can reduce tree photosynthesis and significantly decrease growth, leading to large-scale tree death in severe cases. This can cause degradation of mangrove ecosystems and result in incalculable economic, ecological, and social losses in coastal areas. Therefore, it is urgent to establish a comprehensive monitoring and early warning system and implement integrated management measures.

[0003] Currently, control measures for the teak moth mainly include chemical control, manual control, and biological control. While chemical pesticides such as isodrin, carbaryl, and azadirachtin have some effect, the long-term use of chemical pesticides on mangroves, a nationally protected tree species, not only causes environmental pollution and damage to non-target organisms but may also induce increased pesticide resistance in pests. Manual removal of larvae is time-consuming, labor-intensive, and inefficient, making it difficult to effectively control pest populations. Biological control techniques, with their advantages of precision, environmental friendliness, and sustainability, are more suitable for widespread application. Natural enemies of the teak moth include the giant wasp *Brachymeria lasus* and the trichogramma raoi. Although the use of natural enemies has achieved some success, the high requirements and costs of breeding and releasing them, coupled with the sudden and unexpected nature of teak moth infestations, make it difficult for natural enemies to cope with influxes in a short period, thus significantly limiting their practical application. Microbial agents such as nucleopolyhedrovirus are also widely used for larval control. This virus can spread horizontally to infect neighboring susceptible teak moth populations and can also be vertically inherited by offspring. This unique mixed transmission mode is conducive to the large-scale colonization of the virus. However, effective biological control measures for adult teak moths are still lacking.

[0004] Insect sex pheromones are chemical signaling substances produced and released by adult insects after reaching sexual maturity. They attract or stimulate courtship and mating behaviors in individuals of the same species. As crucial communication signals in insect courtship, sex pheromones exhibit a particularly prominent characteristic—high specificity. This specificity is not only reflected in the fact that sex pheromones can precisely attract individuals of the same species, effectively avoiding confusion with other species, but also ensures that insects can accurately and efficiently complete courtship and mating behaviors in complex and ever-changing natural environments, playing an irreplaceable role in the reproduction and survival of the species.

[0005] Insect sex pheromone-related technologies and products have significant advantages such as high sensitivity, strong selectivity, harmlessness to natural enemies, and environmental protection. They have been widely used in insect monitoring, mating interference, pest quarantine, and mass trapping, achieving good economic and ecological benefits.

[0006] Patent publication number CN116210499A discloses a report on the control of mangrove pests using liquid plant glue, insect sex pheromone reagent, and biological agents. However, the insect sex pheromone mentioned is at least one of the sex pheromones of Populus clearwing moth, Mongolian wood-boring moth, Sophora japonica leafroller, Populus dwarf clearwing moth, beet moth, and cutworm, but does not include the sex pheromone of the teak moth, and has no attraction effect on the teak moth.

[0007] To date, research on sex pheromones in camel moths is still in its infancy. The composition of the teak camel moth's sex pheromone remains unanalyzed, and there is a lack of sex pheromone attractant products on the market. Against this backdrop, identifying the teak camel moth's sex pheromone and developing corresponding sex pheromone attractants represents the first exploratory practice in China to target this invasive alien pest with sex pheromones. This research not only has the potential to fill the gap in camel moth sex pheromone research but also provides solid theoretical support for developing efficient and precise teak camel moth sex pheromone attractants, thereby achieving accurate monitoring and green control of this pest. Summary of the Invention

[0008] This invention provides a teak moth sex pheromone, wherein the sex pheromone component includes trans-9-docosahexaene. Preferably, the sex pheromone component further includes one or more of trans-7-cis-9-docosahexaene, cis-8-cis-10-docosahexaene, and trans-6-trans-8-docosahexaene.

[0009] Specifically, the teak camel moth sex pheromone also includes one or more of the following (1)-(8):

[0010] (1) The structure of trans-9-docoene is ;

[0011] (2) The structure of trans-7-cis-9-docosadiene is: ;

[0012] (3) The structure of cis-8-cis-10-docosadiene is: ;

[0013] (4) The structure of trans-6-trans-8-docosadiene is: ;

[0014] (5) The preparation method of trans-9-docoene includes: using nonyltriphenylphosphine bromide and dodecaldehyde as raw materials, and butyllithium (BuLi) as alkaline catalyst, it is prepared by Wittig-Schlosser reaction;

[0015] (6) The preparation method of trans-7-cis-9-tetradecadiene includes: using dodecyltriphenylphosphine bromide and trans-2-nonenal as raw materials, and butyllithium as an alkaline catalyst, it is prepared by Wittig reaction;

[0016] (7) The preparation method of cis-8-cis-10-tetradecadiene includes: using undecyltriphenylphosphine bromide and cis-2-decenal as raw materials, and butyllithium as an alkaline catalyst, it is prepared by Wittig reaction;

[0017] (8) The preparation method of trans-6-trans-8-tetracarbodiene includes: using tridecyltriphenylphosphine bromide and trans-2-octenal as raw materials, and butyllithium as an alkaline catalyst, to prepare it by Wittig-Schlosser reaction.

[0018] The present invention also provides a teak moth sex pheromone attractant, wherein the effective components of the attractant include trans-9-docosahexaene, trans-7-cis-9-docosadiene, cis-8-cis-10-docosadiene and trans-6-trans-8-docosadiene in a mass ratio of 1:0 to 1:0 to 1:0 to 1:0 to 1.

[0019] Preferably, in the attractant, the mass ratio of the active ingredients trans-9-docrene, trans-7-cis-9-docrene, cis-8-cis-10-docrene and trans-6-trans-8-docrene is 1:1:0.25:0.25.

[0020] The present invention also provides an application of the aforementioned teak moth sex pheromone or attractant in the control of the teak moth.

[0021] Specifically, the application involves adding the teak moth sex pheromone or attractant to a carrier to prepare a lure, and then placing the lure into a trap for use.

[0022] The application also includes one or more of the following (1)-(3):

[0023] (1) The carrier is one or more of polyethylene pipe, polyvinyl chloride pipe, polyethylene bottle, polyethylene slow-release bag, polyvinyl chloride slow-release bag, and rubber stopper;

[0024] (2) The trap is a boat-shaped trap;

[0025] (3) Disperse and hang multiple of the traps in the area infested by the teak moth.

[0026] Preferably, the carrier is a rubber stopper. The trap is suspended at a height of 1.5m above the ground, and / or the traps are spaced 50m apart.

[0027] The beneficial effects of this invention include: the teak moth sex pheromone provided by this invention, comprising trans-9-docoene, can attract large numbers of adult teak moths, especially the attractant composed of trans-9-docoene, trans-7-cis-9-docodiene, cis-8-cis-10-docodiene, and trans-6-trans-8-docodiene in a mass ratio of 1:0.25:0.25:0.5, which exhibits the most outstanding trapping effect. This invention provides a pollution-free, green control technology for the teak moth, enabling pest monitoring and harmless control. It has the advantages of being environmentally friendly and pollution-free, and has significant ecological and economic benefits. Attached Figure Description

[0028] Figure 1 EAG response diagram of male teak moth to gonadal extracts from female moths at different time periods;

[0029] Figure 2 EAD reaction diagram of male teak moth to gonadal extract of female moth;

[0030] Figure 3 Gas chromatogram of the active ingredient in the gonadal extract of the female teak moth;

[0031] Figure 4 EAG reaction of male teak moth to 21-carbon monoene compounds;

[0032] Figure 5 EAG reaction of male teak moth to cis-trans and trans-cis configurations of docosahexaene compounds;

[0033] Figure 6 EAG reaction of male teak moth to cis-cis configuration 21-carbodiene compounds;

[0034] Figure 7 EAG reaction of male teak moth to trans-trans carbodiene compounds;

[0035] Figure 8 EAD reaction diagrams of male teak moths to trans-9-dococene, trans-7-cis-9-dococadiene, cis-8-cis-10-dococadiene and trans-6-trans-8-dococadiene.

[0036] Figure 9 This is a diagram illustrating the effect of the rubber stopper as a slow-release carrier on the trapping of the teak moth in Example 4. Detailed Implementation

[0037] 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.

[0038] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0039] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0040] Example 1: Extraction of sex pheromone components from the teak moth

[0041] (1) Extraction of gonadal extracts at different time periods

[0042] Solvent extraction sampling: Unmated female teak moths, 1-2 days after emergence, were selected and subjected to dark periods of 3h, 6h, 9h, 12h, and 15h. When extracting glands from female teak moths, the abdomen was gently squeezed to expose the sex pheromone glands. The glands were removed with clean tweezers and placed on filter paper to remove body fluids and fat bodies. Twenty glands were then placed in a miniature pointed-bottom glass tube, and 100μL of n-hexane was injected. Each group consisted of 10 female moths, with five replicates per group. After 40 minutes of extraction, the n-hexane extract was aspirated, concentrated to 1μL using high-purity nitrogen, sealed in a capillary glass tube, labeled, and stored at -20℃ for later use.

[0043] (2) Analysis of EAG from gland extracts of male adult teak moths at different time points

[0044] Unmated, active male teak moths, 1-2 days old after emergence, were selected. The antennae were trimmed by 1-2 mm to expose the medulla. The antennae were fixed to both ends of an electrode with conductive adhesive. The electrode was connected to a signal amplifier via a silver-silver chloride wire and placed in a humidified airflow (300 mL / min). Potential changes were recorded and analyzed using a Syntech EAG system. 20 μL of gland extracts prepared in step (1) of this embodiment at different time points were evenly dropped onto a 6 cm × 0.5 cm filter paper as a carrier for the odor source. The gland extracts were measured in ascending order of dark period treatment time, with each odor source stimulation lasting 0.5 s and an interval of at least 60 s between stimulations. The absolute value of the EAG reaction was measured before and after each measurement using n-hexane as a blank control.

[0045] EAG reaction results showed that gonadal extracts from teak moths at different treatment times could elicit electrophysiological responses in the antennae of male moths. The gonadal extracts treated during the 12-hour dark period elicited the strongest EAG response, which was significantly higher than the treatments at other time periods. Figure 1 ).

[0046] Example 2: Identification of sex pheromone components of the teak moth

[0047] (1) GC-EAD analysis of gland extracts from male adult teak moths

[0048] Gonadal extracts treated for 12 hours in the dark were analyzed by GC-EAD. An Agilent 7890A gas chromatograph-Syntech antennal potentiometric analyzer (GC-EAD) equipped with a DB-5MS capillary column was used. High-purity helium was used as the carrier gas at a flow rate of 1 mL / min. The sample was injected splitlessly, and after 1 min, the split valve was opened, allowing 1 μL of sample to be injected. The injection port was set to 250°C, and the temperature was increased according to a specific program. The antennal potentiometer was operated under the set conditions. Male moth antennae were treated as in Example 1. Data were collected and analyzed using GC-EAD software. Different male moth antennae were used each time, and each sample was measured three times.

[0049] The results are as follows Figure 2 As shown, through EAD analysis, four active component peaks (peak 1, peak 2, peak 3 and peak 4) were screened from the n-hexane extract of the glands of female teak moths, which could induce significant electrophysiological responses in the antennae of male teak moths.

[0050] (2) GC-MS identification of compound components

[0051] Glandular extracts were analyzed using an Agilent 7890B-5977 GC-MS system. The column was a DB-5MS (30m × 0.25mm × 0.25μm), with high-purity helium as the carrier gas. The flow rate was 1 mL / min, and the injection was splitless. After 1 min, the split valve was opened, and 1 μL of sample was injected. The injection port was set to 250℃, and the temperature was increased according to a specific program. MS conditions: EI ion source, electron energy 70 eV, transfer line 250℃, ion source 220℃, scan range 20-550 amu.

[0052] GC-MS analysis showed that the molecular weight of active component peak 1 in the teak moth gonad extract was 294, and based on ion fragment analysis, the structure of this compound was inferred to be a 21-carbon monoene. Active components peaks 2, 3, and 4 all had a molecular weight of 292, and their structures are likely 21-carbon conjugated dienes.

[0053] (3) Synthesis of icosenes and icosene conjugated dienes

[0054] cis-5-Ceicosene (Z5-21Hy): Prepared by the Wittig reaction. Amyltriphenylphosphine bromide (8.26 g, 0.02 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), hexadecaldehyde (4.8 g, 0.02 mol). Product: 4.29 g, yield: 73%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.32 (30H, m), 2.02 (4H, m), 5.35 (2H, m). GC-MS (m / z): 294.

[0055] trans-5-docoene (E5-21Hy): prepared by the Wittig-Schlosser reaction. Amyltriphenylphosphine bromide (8.26 g, 0.02 mol), n-BuLi (0.044 mol, 17.6 mL, 2.5 M), hexadecaldehyde (4.8 g, 0.02 mol). Product: 3 g, yield: 51%. 1 H NMR (500 Hz, CDCl3) delta: 0.88 (6H, m), 1.26-1.36 (30H, m), 1.97 (4H, m), 5.39 (2H, m). GC-MS (m / z): 294.

[0056] cis-6-docoene (Z6-21Hy): Prepared by the Wittig reaction. Hexyltriphenylphosphine bromide (6.94 g, 0.02 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), pentadecylaldehyde (4.52 g, 0.02 mol). Product: 4 g, yield: 68%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.34 (30H, m), 2.01 (4H, m), 5.35 (2H, m). GC-MS (m / z): 294.

[0057] trans-6-docoene (E6-21Hy): prepared by the Wittig-Schlosser reaction. Hexyltriphenylphosphine bromide (6.94 g, 0.02 mol), n-BuLi (0.044 mol, 17.6 mL, 2.5 M), pentadecylaldehyde (4.52 g, 0.02 mol), product 2.82 g, yield 48%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.35 (30H, m), 1.96 (4H, m), 5.39 (2H, m). GC-MS (m / z): 294.

[0058] cis-7-docoene (Z7-21Hy): Prepared by the Wittig reaction. Heptyltriphenylphosphine bromide (8.82 g, 0.02 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), tetradecanal (4.24 g, 0.02 mol). Product: 3.06 g, yield: 52%. 1H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.34 (30H, m), 2.01 (4H, m), 5.35 (2H, m). GC-MS (m / z): 294.

[0059] trans-7-dococarne (E7-21Hy): Prepared by the Wittig-Schlosser reaction. Heptyltriphenylphosphine bromide (8.82 g, 0.02 mol), n-BuLi (0.044 mol, 17.6 mL, 2.5 M), tetradecanal (4.24 g, 0.02 mol). Product: 2.70 g, yield: 46%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.34 (30H, m), 1.96 (4H, m), 5.38 (2H, m). GC-MS (m / z): 294.

[0060] cis-8-docoene (Z8-21Hy): Prepared by the Wittig reaction. Octyltriphenylphosphine bromide (9.1 g, 0.02 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), tridecaaldehyde (3.96 g, 0.02 mol). Product: 2.94 g, yield: 50%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.35 (30H, m), 2.01 (4H, m), 5.35 (2H, m). GC-MS (m / z): 294.

[0061] trans-8-docoene (E8-21Hy): prepared by the Wittig-Schlosser reaction. Octyltriphenylphosphine bromide (9.1 g, 0.02 mol), n-BuLi (0.044 mol, 17.6 mL, 2.5 M), tridecaaldehyde (3.96 g, 0.02 mol). Product: 2.59 g, yield: 44%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.25-1.33 (30H, m), 1.95 (4H, m), 5.37 (2H, m). GC-MS (m / z): 294.

[0062] cis-9-docoene (Z9-21Hy): Prepared by the Wittig reaction. Nonyltriphenylphosphine bromide (9.38 g, 0.02 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), dodecylaldehyde (3.68 g, 0.02 mol). Product: 3.23 g, yield: 55%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.34 (30H, m), 2.01 (4H, m), 5.35 (2H, m). GC-MS (m / z): 294.

[0063] Trans-9-Cephane (E9-21Hy): Prepared using the Wittig-Schlosser reaction. Specifically, nonyltriphenylphosphine bromide (9.38 g, 0.02 mol) was dissolved in THF, and n-BuLi (0.022 mol, 8.8 mL, 2.5 M) was added dropwise at -78 °C. After stirring at room temperature for 1 h, the mixture was cooled again to -78 °C, and dodecanoic acid (3.68 g, 0.02 mol) was added dropwise, followed by n-BuLi (0.022 mol, 8.8 mL, 2.5 M). The reaction was allowed to proceed overnight. After filtering out insoluble matter, water was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, and the solvent was removed under vacuum to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether as the mobile phase to obtain trans-9-cephane (2.70 g, yield 46%). 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.33 (30H), 1.96 (4H, m), 5.38 (2H, m). GC-MS (m / z): 294.

[0064] cis-10-docoene (Z10-21Hy): Prepared by the Wittig reaction. Decyltriphenylphosphine bromide (9.66 g, 0.02 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), undecane (3.4 g, 0.02 mol). Product: 3.18 g, yield: 54%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.33 (30H, m), 2.01 (4H, m), 5.34(2H, m). GC-MS (m / z): 294.

[0065] trans-10-docoene (E10-21Hy): prepared by the Wittig-Schlosser reaction. Decyltriphenylphosphine bromide (9.38 g, 0.02 mol), n-BuLi (0.044 mol, 17.6 mL, 2.5 M), undecanoic acid (3.68 g, 0.02 mol). Product: 2.47 g, yield: 42%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.31 (30H, m), 1.95 (4H, m), 5.38 (2H, m). GC-MS (m / z): 294.

[0066] cis-5-trans-7-docosadiene (Z5E7-21Hy): Prepared by the Wittig-Schlosser reaction. Tetradecyltriphenylphosphine bromide (5.4 g, 0.01 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), cis-2-heptenal (1.12 g, 0.01 mol). Product: 1.34 g, yield: 46%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.25-1.31(26H, m), 2.06 (2H, m), 2.16 (2H, m), 5.29 (1H, m), 5.66 (1H, m), 5.93 (1H,m), 6.28 (1H, m). GC-MS (m / z): 292.

[0067] cis-5-cis-7-docosadiene (Z5Z7-21Hy): Prepared by the Wittig reaction. Tetradecyltriphenylphosphine bromide (5.4 g, 0.01 mol), n-BuLi (0.011 mol, 4.4 mL, 2.5 M), cis-2-heptenal (1.12 g, 0.01 mol). Product: 1.90 g, yield: 65%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.39 (26H. m), 2.17(4H, m), 5.44 (2H, m), 6.24 (2H, m). GC-MS (m / z): 292.

[0068] trans-5-cis-7-docosadiene (E5Z7-21Hy): Prepared by the Wittig reaction. Tetradecyltriphenylphosphine bromide (5.4 g, 0.01 mol), n-BuLi (0.011 mol, 4.4 mL, 2.5 M), trans-2-heptenal (1.12 g, 0.01 mol). Product: 1.93 g, yield: 66%. 1 H NMR (500 Hz, CDCl3) δ: 0.89 (6H, m), 1.26-1.39 (26H, m), 2.09(2H, m), 2.16 (2H, m), 5.30 (1H, m), 5.65 (1H, m), 5.94 (1H, m), 6.29 (1H,m). GC-MS (m / z): 292.

[0069] trans-5-trans-7-docosadiene (E5E7-21Hy): prepared by the Wittig-Schlosser reaction. Tetradecyltriphenylphosphine bromide (5.4 g, 0.01 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), trans-2-heptenal (1.12 g, 0.01 mol). Product: 1.26 g, yield: 43%. 1 H NMR (500 Hz, CDCl3) δ: 0.87 (6H, m), 1.27-1.39(26H, m), 2.05 (4H, m), 5.54 (2H, m), 6.01 (2H, m). GC-MS (m / z): 292.

[0070] cis-6-trans-8-docosadiene (Z6E8-21Hy): Prepared by the Wittig-Schlosser reaction. Tridecyltriphenylphosphine bromide (5.25 g, 0.01 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), cis-2-octenal (1.26 g, 0.01 mol). Product: 1.37 g, yield: 47%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.32(26H, m), 2.08 (2H, m), 2.15 (2H, m), 5.30 (1H, m), 5.65 (1H, m), 5.94 (1H,m), 6.29 (1H, m). GC-MS (m / z): 292.

[0071] cis-6-cis-8-docosadiene (Z6Z8-21Hy): Prepared by the Wittig reaction. Tridecyltriphenylphosphine bromide (5.25 g, 0.01 mol), n-BuLi (0.011 mol, 4.4 mL, 2.5 M), cis-2-octenal (1.26 g, 0.01 mol). Product: 1.89 g, yield: 64%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.40 (26H, m), 2.16(4H, m), 5.44 (2H, m), 6.24 (2H, m). GC-MS (m / z): 292.

[0072] trans-6-cis-8-docosadiene (E6Z8-21Hy): Prepared by the Wittig reaction. Tridecyltriphenylphosphine bromide (5.25 g, 0.01 mol), n-BuLi (0.011 mol, 4.4 mL, 2.5 M), trans-2-octenal (1.26 g, 0.01 mol). Product: 1.84 g, yield: 63%. 1 H NMR (500 Hz, CDCl3) δ: 0.89 (6H, m), 1.26-1.41 (26H, m), 2.08(2H, m), 2.15 (2H, m), 5.30 (1H, m), 5.65 (1H, m), 5.94 (1H, m), 6.29 (1H,m). GC-MS (m / z): 292.

[0073] trans-6-trans-8-cuecodesadiene (E6E8-21Hy): Prepared using the Wittig-Schlosser reaction. Specifically, tridecyltriphenylphosphine bromide (5.25 g, 0.01 mol) was dissolved in THF, and n-BuLi (0.011 mol, 4.4 mL, 2.5 M) was added dropwise at -78 °C. After stirring at room temperature for 1 h, the mixture was cooled again to -78 °C, and trans-2-octenal (1.26 g, 0.01 mol) was added dropwise, followed by n-BuLi (0.011 mol, 4.4 mL, 2.5 M). The reaction was allowed to proceed overnight. After filtering out insoluble matter, water was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, and the solvent was removed under vacuum to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether as the mobile phase to obtain trans-6-trans-8-cuecodesadiene (1.28 g, 45% yield). 1H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.39 (26H, m), 2.04 (4H, m), 5.56 (2H, m), 6.00 (2H, m). GC-MS (m / z): 292.

[0074] cis-7-trans-9-docosadiene (Z7E9-21Hy): Prepared by the Wittig-Schlosser reaction. Dodecyltriphenylphosphine bromide (5.11 g, 0.01 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), cis-2-nonenal (1.4 g, 0.01 mol). Product: 1.40 g, yield: 48%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.38(26H, m), 2.08 (2H, m), 2.15 (2H, m), 5.30 (1H, m), 5.65 (1H, m), 5.94 (1H,m), 6.29 (1H, m). GC-MS (m / z): 292.

[0075] cis-7-cis-9-docosadiene (Z7Z9-21Hy): Prepared by the Wittig reaction. Dodecyltriphenylphosphine bromide (5.11 g, 0.01 mol), n-BuLi (0.011 mol, 4.4 mL, 2.5 M), cis-2-nonenal (1.4 g, 0.01 mol). Product: 1.9 g, yield: 65%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.39 (26H, m), 2.16(4H, m), 6.25 (2H, m). GC-MS (m / z): 292.

[0076] trans-7-cis-9-docosadiene (E7Z9-21Hy): Prepared using the Wittig reaction. Specifically, dodecyltriphenylphosphine bromide (5.11 g, 0.01 mol) was dissolved in THF, and n-BuLi (0.011 mol, 4.4 ml, 2.5 M) was added dropwise at -78°C. After stirring at room temperature for 1 h, the mixture was cooled again to -78°C, and trans-2-nonenal (1.4 g, 0.01 mol) was added dropwise. The reaction was allowed to proceed overnight. After filtering out insoluble matter, water was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, and the solvent was removed under vacuum to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether as the mobile phase to obtain trans-7-cis-9-docosadiene (1.81 g, yield 62%). 1H NMR (500 Hz, CDCl3) δ: 0.87 (6H, m), 1.26-1.39 (26H, m), 2.08 (2H, m), 2.15(2H, m), 5.29 (1H, m), 5.65 (1H, m), 5.94 (1H, m), 6.29 (1H, m). GC-MS (m / z):292.

[0077] trans-7-trans-9-docosadiene (E7E9-21Hy): Prepared by the Wittig-Schlosser reaction. Dodecyltriphenylphosphine bromide (5.11 g, 0.01 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), trans-2-nonenal (1.4 g, 0.01 mol). Product: 1.37 g, yield: 47%. 1 H NMR (500 Hz, CDCl3) delta: 0.87 (6H, m), 1.25-1.38(26H, m), 2.05 (4H, m), 5.57 (2H, m), 6.02 (2H, m). GC-MS (m / z): 292.

[0078] cis-8-trans-10-docosadiene (Z8E10-21Hy): Prepared by the Wittig-Schlosser reaction. Undecyltriphenylphosphine bromide (4.97 g, 0.01 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), cis-2-decenal (1.54 g, 0.01 mol). Product: 1.34 g, yield: 46%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.38 (26H, m), 2.09 (2H, m), 2.15 (2H, m), 5.30 (1H, m), 5.64 (1H, m), 5.94(1H, m), 6.29 (1H, m). GC-MS (m / z): 292.

[0079] cis-8-cis-10-docosadiene (Z8Z10-21Hy): Prepared by the Wittig reaction. Specifically, undecyltriphenylphosphine bromide (4.97 g, 0.01 mol) was dissolved in THF, and n-BuLi (0.011 mol, 4.4 mL, 2.5 M) was added dropwise at -78 °C. After stirring at room temperature for 1 h, the mixture was cooled again to -78 °C, and cis-2-decenal (1.54 g, 0.01 mol) was added dropwise. The reaction was allowed to proceed overnight. After filtering out insoluble matter, water was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, and the solvent was removed under vacuum to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether as the mobile phase. Cis-8-cis-10-docosadiene (1.96 g, yield 67%) was obtained. 1 H NMR (500 Hz, CDCl3) δ: 0.87 (6H, m), 1.26-1.38 (26H, m), 2.16 (4H, m), 5.45(2H, m), 6.24 (2H, m). GC-MS (m / z): 292.

[0080] trans-8-cis-10-docosadiene (E8Z10-21Hy): Prepared by the Wittig reaction. Undecyltriphenylphosphine bromide (4.97 g, 0.01 mol), n-BuLi (0.011 mol, 4.4 mL, 2.5 M), trans-2-decenal (1.54 g, 0.01 mol). Product: 1.87 g, yield: 64%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.38 (26H, m), 2.08 (2H, m), 2.14 (2H, m), 5.30 (1H, m), 5.65 (1H, m), 5.94 (1H, m), 6.29(1H, m). GC-MS (m / z): 292.

[0081] trans-8-trans-10-cuicocarbodiene (E8E10-21Hy): prepared by the Wittig-Schlosser reaction. Undecyltriphenylphosphine bromide (4.97 g, 0.01 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), trans-2-decenal (1.54 g, 0.01 mol). Product: 1.31 g, yield: 45%. 1 H NMR (500 Hz, CDCl3) delta: 0.87 (6H, m), 1.26-1.38 (26H, m), 2.04 (4H, m), 5.56 (2H, m), 6.00 (2H, m). GC-MS (m / z): 292.

[0082] cis-9-trans-11-docosadiene (Z9E11-21Hy): Prepared by the Wittig-Schlosser reaction. Decyltriphenylphosphine bromide (4.83 g, 0.01 mol), n-BuLi (0.022 mol, 8.8 mL, 2.5 M), cis-2-undecenal (1.68 g, 0.01 mol). Product: 1.40 g, yield: 48%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.26-1.38 (26H, m), 2.09 (2H, m), 2.15 (2H, m), 5.30 (1H, m), 5.65 (1H, m), 5.94(1H, m), 6.29 (1H, m). GC-MS (m / z): 292.

[0083] cis-9-cis-11-docosadiene (Z9Z11-21Hy): Prepared by the Wittig reaction. Decyltriphenylphosphine bromide (4.83 g, 0.01 mol), n-BuLi (0.011 mol, 4.4 mL, 2.5 M), cis-2-undecenal (1.68 g, 0.01 mol). Product: 1.87 g, yield: 64%. 1 H NMR (500 Hz, CDCl3) delta: 0.88 (6H, m), 1.26-1.38 (26H, m), 2.16 (4H, m), 5.44 (2H, m), 6.24 (2H, m). GC-MS (m / z): 292.

[0084] trans-9-cis-11-docosadiene (E9Z11-21Hy): Prepared by the Wittig reaction. Decyltriphenylphosphine bromide (4.83 g, 0.01 mol), n-BuLi (0.011 mol, 4.4 mL, 2.5 M), trans-2-undecenal (1.68 g, 0.01 mol). Product: 1.93 g, yield: 66%. 1 H NMR (500 Hz, CDCl3) δ: 0.88 (6H, m), 1.27-1.40 (26H, m), 2.09 (2H, m), 2.15 (2H, m), 5.29 (1H, m), 5.65 (1H, m), 5.94 (1H, m), 6.29(1H, m). GC-MS (m / z): 292.

[0085] trans-9-trans-11-docosadiene (E9E11-21Hy): Prepared by the Wittig-Schlosser reaction. Decyltriphenylphosphine bromide (4.83 g, 0.01 mol), n-BuLi (0.011 mol, 4.4 mL, 2.5 M), trans-2-undecenal (1.68 g, 0.01 mol). Product: 1.40 g, yield: 48%. 1 H NMR (500 Hz, CDCl3) delta: 0.89 (6H, m), 1.27-1.39 (26H, m), 2.06 (4H, m), 5.57 (2H, m), 5.99 (2H, m). GC-MS (m / z): 292.

[0086] (4) Gas phase analysis of icosene and icosene conjugated diene compounds with teak moth gland extract

[0087] The synthesized icosene and icosene conjugated diene compounds were analyzed by gas chromatography (Agilent 7890A) using a DB-5MS column (30m × 0.25mm × 0.25μm). The injection volume was 1 μL, the injection port temperature was 250℃, and the temperature program was as follows: initial temperature 40℃, hold for 5 min, increase to 210℃ at 1℃ / min, hold for 1 min, increase to 280℃ at 20℃ / min, hold for 10 min.

[0088] Gas chromatography analysis results as follows Figure 3 As shown, the extract of the glands of the teak moth may contain a variety of 2,1-carboene and 2,1-carboene conjugated diene compounds, so it is difficult to find the active ingredient peak by simply comparing retention times.

[0089] The aforementioned candidate sex pheromone compounds can be divided into four categories: I. docosahexanes, II. cis-trans and trans-cis docosahexanes, III. cis-cis docosahexanes, and IV. trans-trans docosahexanes. The EAG and EAD methods were subsequently used to test these four categories of compounds in order to screen for active ingredients.

[0090] (5) EAG test of 21-carbon monoenes and 21-carbon conjugated dienes

[0091] A 0.1 μg / μL solution of a 21-carbon monoene and a 21-carbon conjugated diene compound was prepared using n-hexane as a solvent. A filter paper strip was fixed to the inner wall of the sterilizing pipette tip, and 10 μL of the sample was added, with n-hexane used as a control. The pipette tip was connected to a stimulation gas flow device, with the tip inserted into the small hole of a Pasteur tube. The stimulation gas flow rate was 40 mL / min, with a continuous flow rate of 1200 mL / min, each stimulation lasting 0.3 s, with a 60 s interval. Treatment of the antennae of male teak moths was performed according to Example 1.

[0092] EAG results showed that male antennae exhibited larger EAG response values ​​to trans-9-dococene (E9-21Hy), trans-7-cis-9-dococadiene (E7Z9-21Hy), cis-8-cis-10-dococadiene (Z8Z10-21Hy), and trans-6-trans-8-dococadiene (E6E8-21Hy). Figure 4-7 These four compounds may be the active components of the sex pheromone of the teak camel moth.

[0093] (6) GC-EAD analysis of four standard samples by male adult teak moths

[0094] Trans-9-dococarne, trans-7-cis-9-dococardiene, cis-8-cis-10-dococardiene, and trans-6-trans-8-dococardiene were prepared into hexane solutions (trans-9-dococarne 50 ng / μL, trans-7-cis-9-dococardiene 100 ng / μL, cis-8-cis-10-dococardiene 40 ng / μL, and trans-6-trans-8-dococardiene 20 ng / μL) for EAD analysis. A DB-5MS column (30 m × 0.25 mm × 0.25 μm) was used. The injection volume was 1 μL, the injection port temperature was 250 °C, and the temperature program was: initial temperature 150 °C, hold for 1 min, increase to 280 °C at 10 °C / min, hold for 8 min. The results showed that all four compounds induced an EAD response in male moths. Figure 8 ).

[0095] Example 3: Field trapping experiment using teak moth sex pheromone attractants

[0096] (1) Experiments with sex pheromone attractants of different components

[0097] A teak moth sex pheromone attractant was prepared, comprising four sex pheromone components: trans-9-dococarne (A), trans-7-cis-9-dococardiene (B), cis-8-cis-10-dococardiene (C), and trans-6-trans-8-dococardiene (D). The sex pheromone components were added to rubber stoppers at the mass ratios shown in Table 1 to prepare lures (compounds with insufficient mass in the formula were prepared as dichloromethane solutions and added dropwise). Each lure was placed in a boat-shaped trap, with each lure containing a total of 1000 μg of active ingredient. Trapping experiments were conducted in teak moth-infested areas of Zhanjiang, Guangdong Province, from May 8th to June 7th, 2024. Traps containing lures containing teak moth sex pheromone attractants were suspended on branches of *Avicennia marina* trees, 1.5 m above the ground, with traps spaced 50 m apart. Six traps were set up for each group as a replicate experiment, and a blank control group was also included. Observe once a week, count the adult insects and replace the sticky traps.

[0098] Table 1. Trapping experimental data of different attractant treatment groups

[0099]

[0100] The data in Table 1 show that: (1) Through the unit components (treatments 1-4), it can be seen that the trapping effect of trans-9-docoene (A) is better than that of the other three components; (2) In the binary components (treatments 5-10), the trapping effect of trans-9-docoene (A) and trans-7-cis-9-docodiene (B) mixed in equal proportions is significantly higher than that of other binary components; and the binary components containing trans-9-docoene (A) are significantly higher than those of other binary components that do not contain trans-9-docoene (A); (3) Ternary components (treatments 11-1 4) The sex pheromone attractant had a significantly better trapping effect than the single-component and binary-component formulations. The formulation containing trans-9-docoene (A) and trans-7-cis-9-docodiene (B) had the highest trapping effect and was significantly better than the other ternary-component formulations. The ternary-component formulation containing trans-9-docoene (A) was significantly better than the ternary-component formulation without trans-9-docoene (A). (4) The quaternary sex pheromone attractant (treatment 15) had the most outstanding trapping effect and was significantly better than the single-component, binary-component, and ternary-component formulations. The above results show that the trapping effect of the formulation containing trans-9-docoene (A) is significantly better than other formulations of the same type that do not contain this component, and the quaternary sex pheromone attractant has the most outstanding attraction effect on the teak moth.

[0101] (2) Trapping experiments with sex pheromone attractants of different proportions

[0102] A teak moth sex pheromone attractant was prepared, comprising four sex pheromone components: trans-9-dococarne (A), trans-7-cis-9-dococardiene (B), cis-8-cis-10-dococardiene (C), and trans-6-trans-8-dococardiene (D). The sex pheromone components were added to rubber stoppers at the mass ratios shown in Table 2 to form lures, which were then placed in boat-shaped traps. Each lure contained a total of 1000 μg of active ingredient. The specific preparation method was the same as step (1) of this embodiment. Trapping experiments were conducted in teak moth-infested areas of Zhanjiang, Guangdong Province, from July 6th to August 29th, 2024.

[0103] Table 2. Trapping experimental data of attractants composed of four components in different proportions.

[0104]

[0105] The results are shown in Table 2. All four-component sex pheromone attractants with different proportions were effective in attracting male teak moths. When the mass ratio of cis-8-cis-10-docosadiene (C) and trans-6-trans-8-docosadiene (D) in the four-component lure was reduced to 0.5–0.25, the trapping effect of the four-component sex pheromone attractant was enhanced, especially at a mass ratio of 1:1:0.25:0.25, where the trapping effect was the best and the number of moths trapped was significantly higher than in the other treatment groups. This has important application value in the monitoring and control of teak moths.

[0106] Example 4: Screening of the optimal release carrier for the attractant

[0107] The teak moth sex pheromone attractant prepared in treatment group 7 of Example 3 was used, and lures were prepared using three slow-release carriers: rubber stoppers (A1, A2, A3), polyethylene tubes (B1, B2, B3), and polyvinyl chloride tubes (C1, C2, C3). The lures were placed in trapping devices with the same structure as in Example 3 for testing. The average spacing between traps was 50 m, and the lure height above the ground was 1.5 m. Each slow-release carrier was tested in triplicate. The trapping experiment was conducted in the teak moth-infested area of ​​Zhanjiang, Guangdong Province, from September 24th to October 29th, 2024. After the traps were placed, the number of adult teak moths captured was investigated every 6 days, and the trap positions were randomly changed. The results are shown in Table 3.

[0108] Table 3. Effects of different release carriers on the trapping effect of teak moth.

[0109]

[0110] As can be seen from Table 3, the optimal attraction of the teak camel moth sex pheromone attractant is achieved when the rubber stopper is used as the slow-release carrier. Figure 9 ).

Claims

1. A teak moth sex pheromone attractant, characterized in that, The active ingredients of the attractant include trans-9-docosahexene, trans-7-cis-9-docosadiene, cis-8-cis-10-docosadiene, and trans-6-trans-8-docosadiene in a mass ratio of 1:0 to 1:0 to 1:0 to 1:0 to 1, wherein the mass ratio of trans-7-cis-9-docosadiene, cis-8-cis-10-docosadiene, and trans-6-trans-8-docosadiene is not simultaneously 0.

2. The teak moth sex pheromone attractant according to claim 1, characterized in that, In the attractant, the mass ratio of the active ingredients trans-9-dococarne, trans-7-cis-9-dococardiene, cis-8-cis-10-dococardiene and trans-6-trans-8-dococardiene is 1:1:0.25:0.

25.

3. The application of the attractant according to claim 1 or 2 in the control of teak moth.

4. The application according to claim 3, characterized in that, The application involves adding the attractant to a carrier to prepare a teak moth lure, and then placing the lure into a trap for use.

5. The application according to claim 4, characterized in that, Includes one or more of the following (1)-(3): (1) The carrier is one or more of polyethylene pipe, polyvinyl chloride pipe, polyethylene bottle, polyethylene slow-release bag, polyvinyl chloride slow-release bag, and rubber stopper; (2) The trap is a boat-shaped trap; (3) Disperse and hang multiple of the traps in the area infested by the teak moth.

6. The application according to claim 5, characterized in that, The carrier is a rubber stopper.

7. The application according to claim 5, characterized in that, The traps are suspended at a height of 1.5m above the ground, and / or the traps are spaced 50m apart.

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