Cimex lectularius sex pheromone, lure core, and preparation method and application thereof

Abstract

The present application relates to the technical field of pest control, and provides a sex pheromone of corymbitatus, a lure core and a preparation method and application. The present application identifies the chemical components of the sex pheromone of corymbitatus for the first time through experimental analysis on the natural sex pheromone of female corymbitatus, i.e. (R)-6-acetyloxyhex-2-ol butyrate and (R)-3-acetyloxy butyric acid hexyl ester, both of which are new compounds. The combination of the substances has a strong attraction to male corymbitatus and can be applied to the biological control of corymbitatus. The lure core provided by the present application has good slow release, long effective period, good attraction effect, and is non-toxic and harmless, without the risk of pesticide residues and no impact on beneficial insects in tea gardens. The present application provides a new method for the biological control of corymbitatus and is suitable for tea gardens damaged by corymbitatus, especially for organic tea gardens.

Description

Technical Field

[0001] This invention relates to the field of pest control technology, and in particular to the sex pheromone of the cinchona mirid bug, the lure, its preparation method, and its application. Background Technology

[0002] The cinchona horned bug (Helopeltis cinchonae), belonging to the family Miridae in the order Hemiptera, damages more than 60 plant species, including tea trees, cinchona trees, and peppers. It occurs in tea gardens in Guangxi, Yunnan, Hainan, Guizhou, Guangdong, Tibet, and Jiangxi provinces of my country, with Guangdong and Yunnan being the dominant species, exhibiting widespread and severe damage. Typically, the insect, whether nymph or adult, pierces tender leaves, buds, and stems with its mouthparts to suck sap and inject toxic saliva, causing damage to the tissue around the feeding hole, forming brown circular spots that eventually develop into dark brown sunken spots and dry out. Affected leaves curl, deform, and rot, threatening normal tea production in Guangdong and Yunnan. Currently, there is a lack of scientific research on the control of the cinchona horned bug in China, and no effective control measures exist.

[0003] Insect sex pheromones are trace amounts of chemical substances secreted by specific organs of a particular sex within the same insect species. These pheromones can be detected by the sensory organs of opposite-sex individuals of the same species, triggering behavioral responses or physiological effects (such as courtship, directional mating, and mating). Once an insect's sex pheromone is identified, it has several applications. The first is insect monitoring: the presence of target insects within sex pheromone traps accurately reflects the presence of target insects in a corresponding area and the hatching status of the next generation of larvae. Using sex pheromones for insect monitoring can guide chemical pesticide application, such as determining control thresholds and timing. The second application is mating disorientation: artificially releasing sex pheromones creates a scent source, causing insects to receive incorrect signals during courtship communication, thereby delaying, reducing, or preventing mating. The third application is mass trapping: attracting large numbers of insects of one sex or both sexes using sex pheromones, then using large-capacity traps or chemical pesticides to eliminate the attracted insects.

[0004] Currently, besides chemical pesticides, there are no other effective measures to control the cinchona horned bug. The use of chemical pesticides easily leads to excessive pesticide residues in tea leaves, and repeated use can also lead to pesticide resistance. Therefore, sex pheromones are a promising control technology; however, there are currently no reports on sex pheromones for the cinchona horned bug in this field. Summary of the Invention

[0005] In view of this, the present invention provides a sex pheromone for the cinchona horned bug, a lure, a preparation method, and its application. This invention is the first to propose a sex pheromone component for the cinchona horned bug, which has a good attraction effect on the bug, enabling highly efficient control of the bug, and is non-toxic, harmless, and does not produce pesticide residues.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] The sex pheromones of the cinchona horn mirid bug include (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate.

[0008] Preferably, the mass ratio of (R)-6-acetoxyhexyl-2-ol butyrate to (R)-3-acetoxyhexyl butyrate is (1-10):(1-2).

[0009] Preferably, it is used in the form of a racemic mixture other than (R)-6-acetoxyhexyl-2-ol butyrate.

[0010] This invention also provides a method for preparing the sex pheromone of the cinchona horn mirid bug described above, wherein the preparation method of the (R)-6-acetoxyhexyl-2-ol butyrate includes the following steps:

[0011] Acetyl chloride, 1,5-hexanediol, N,N-diisopropylethylamine and an organic solvent were mixed and subjected to a first esterification reaction to give 1-acetoxy-5-hydroxyhexane;

[0012] The 1-acetoxy-5-hydroxyhexane, vinyl butyrate, Candida antarcticis immobilized lipase and organic solvent were mixed and subjected to an enzymatic reaction to obtain (R)-6-acetoxyhex-2-ol butyrate.

[0013] The preparation method of (R)-3-acetoxybutyrate hexyl ester includes the following steps:

[0014] (R)-3-hydroxybutyric acid, n-hexanol and an acidic catalyst were mixed and subjected to a second esterification reaction to obtain (R)-3-hydroxybutyrate hexyl ester;

[0015] The (R)-3-hydroxybutyrate hexyl ester, acetic anhydride and pyridine were mixed and subjected to a third esterification reaction to obtain (R)-3-acetoxybutyrate hexyl ester.

[0016] Preferably, the preparation method of the racemic form of (R)-6-acetoxyhexyl-2-ol butyrate includes the following steps:

[0017] A fourth esterification reaction was carried out by mixing 1-acetoxy-5-hydroxyhexane, n-butyryl chloride, pyridine and an organic solvent to give 6-acetoxyhex-2-ol butyrate.

[0018] The present invention also provides a cinchona barbadensis lure, comprising a slow-release carrier and an active component loaded on the slow-release carrier, wherein the active component is the cinchona barbadensis sex pheromone described in the above scheme or the cinchona barbadensis sex pheromone prepared by the preparation method described in the above scheme.

[0019] Preferably, the sustained-release carrier is made of PVC; the loading of active components on a single cinchona barbadensis lure is 2500–3500 μg.

[0020] The present invention also provides a method for preparing the cinchona horned bug lure described in the above-mentioned scheme, comprising the following steps:

[0021] The sex pheromone of the cinchona viper was loaded onto a sustained-release carrier to obtain a cinchona viper lure.

[0022] Preferably, the cinchona horned bug sex pheromone is used after being dissolved; the solvent for dissolving is dichloromethane.

[0023] The present invention also provides the application of the cinchona mirid bug sex pheromone described in the above-described scheme or the cinchona mirid bug lure described in the above-described scheme in the control of cinchona mirid bugs.

[0024] This invention provides the sex pheromone of the cinchona horned bug, comprising (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate. Through a series of experimental analyses of the natural sex pheromone of female cinchona horned bugs, this invention identifies for the first time the chemical components of its sex pheromone—(R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate—both novel compounds. Furthermore, this combination of substances exhibits a strong attraction to male cinchona horned bugs and can be applied to the biological control of this pest.

[0025] This invention also provides a cinchona leafminer bug lure, its preparation method, and its application. This invention utilizes the cinchona leafminer bug sex pheromone as an active component loaded onto a slow-release carrier, resulting in a lure with good slow-release properties, long-lasting effect, and excellent attraction. Compared to chemical control methods, using the lure of this invention to control cinchona leafminer bugs has the following advantages: 1. The sex pheromone component is non-toxic, not directly applied to tea trees, eliminating pesticide residue risks on tea leaves, and is harmless to beneficial insects in tea gardens. 2. It is highly effective in attracting and killing male bugs, directly killing a large number of male adults that damage tea leaves, while simultaneously disrupting the male-to-female ratio, reducing mating success rates, and indirectly controlling the next generation of nymphs from damaging tea trees. 3. The lure uses a milligram-level sex pheromone content, making it highly efficient, and its effect lasts for up to 30 days, maintaining long-term suppression of male bug populations with long-term use. This invention provides a new method for the biological control of the cinchona horned bug, which is applicable to tea gardens infested with cinchona horned bugs, and is especially suitable for use in organic tea gardens. Detailed Implementation

[0026] The present invention provides the sex pheromone of the cinchona horn mirid bug, comprising (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate.

[0027] In this invention, the structural formula of (R)-6-acetoxyhexyl-2-ol butyrate is shown in Formula I, and the structural formula of (R)-3-acetoxyhexyl butyrate is shown in Formula II:

[0028]

[0029] In this invention, the mass ratio of (R)-6-acetoxyhexyl-2-ol butyrate to (R)-3-acetoxyhexyl butyrate is preferably (1-10):(1-2), more preferably (1-5):(1-1.5), and most preferably 1:1.

[0030] In this invention, the (R)-6-acetoxyhexyl-2-ol butyrate can also be used in racemic form; the racemic form includes both R and S configurations, resulting in lower preparation costs and greater practical application value. The ratio of the R and S configuration products in the racemic form is 1:1. In specific embodiments of this invention, when using a racemic form, it is preferable to set the amount of the racemic form to twice the mass of pure R-configuration 6-acetoxyhexyl-2-ol butyrate.

[0031] The present invention also provides a method for preparing the sex pheromone of the cinchona horn mirid bug described in the above scheme, including a method for preparing (R)-6-acetoxyhexyl-2-ol butyrate and a method for preparing (R)-3-acetoxyhexyl butyrate, which are described below.

[0032] In this invention, the preparation method of (R)-6-acetoxyhexyl-2-ol butyrate includes the following steps:

[0033] Acetyl chloride, 1,5-hexanediol, N,N-diisopropylethylamine and an organic solvent were mixed and subjected to a first esterification reaction to give 1-acetoxy-5-hydroxyhexane;

[0034] The 1-acetoxy-5-hydroxyhexane, vinyl butyrate, Candida antarcticis immobilized lipase, and organic solvent were mixed and subjected to an enzymatic reaction to obtain (R)-6-acetoxyhex-2-ol butyrate.

[0035] In this invention, the synthetic route for (R)-6-acetoxyhexyl-2-ol butyrate is as follows:

[0036]

[0037] Among them: (i) acetyl chloride / N,N-diisopropylethylamine / dichloromethane; (ii) Candida antarctic immobilized lipase / ether (59%); (iii) n-butyryl chloride / pyridine / dichloromethane.

[0038] The method of the present invention will be described in detail below with reference to the synthetic route.

[0039] This invention involves a first esterification reaction of acetyl chloride, 1,5-hexanediol, N,N-diisopropylethylamine, and an organic solvent to obtain 1-acetoxy-5-hydroxyhexane. In this invention, the molar ratio of acetyl chloride, 1,5-hexanediol, and N,N-diisopropylethylamine is preferably 3–5:3–5:5–10, more preferably 4.1:4:8. The organic solvent used for the first esterification reaction is preferably a haloalkane, more preferably dichloromethane. This invention does not have special requirements regarding the amount of organic solvent used, as long as it ensures the smooth progress of the reaction. The temperature of the first esterification reaction is preferably -80 to -45°C, more preferably -78°C, and the time is preferably 0.5 to 24 hours, more preferably 3 hours. The first esterification reaction is preferably carried out under stirring conditions. This invention does not have special requirements regarding the source of the 1,5-hexanediol; it can be prepared using methods well known to those skilled in the art or a commercially available product.

[0040] After the first esterification reaction, the reaction is preferably quenched with brine, and then the resulting reaction solution is extracted with diethyl ether. The resulting diethyl ether layer is then washed, dried, and rotary evaporated to obtain crude 1-acetoxy-5-hydroxyhexane. The crude 1-acetoxy-5-hydroxyhexane is then subjected to column chromatography, concentration, and distillation to obtain purified 1-acetoxy-5-hydroxyhexane. In this invention, the washing agent is preferably brine; the drying agent is preferably anhydrous magnesium sulfate; and the eluent for column chromatography is preferably a mixed solvent of petroleum ether and diethyl ether, wherein the volume ratio of petroleum ether to diethyl ether in the mixed solvent is preferably 6:4.

[0041] After obtaining 1-acetoxy-5-hydroxyhexane, the present invention mixes the 1-acetoxy-5-hydroxyhexane, vinyl butyrate, Candida antarctic immobilized lipase, and an organic solvent to carry out an enzymatic reaction to obtain (R)-6-acetoxyhex-2-ol butyrate. In the present invention, the molar ratio of 1-acetoxy-5-hydroxyhexane to vinyl butyrate is preferably 3-5:3-5, more preferably 3.3:4; the mass ratio of 1-acetoxy-5-hydroxyhexane to Candida antarctic immobilized lipase is preferably 10-15:1, more preferably 13:1; the organic solvent used for the enzymatic reaction is preferably an ether solvent, more preferably diethyl ether; the present invention does not have special requirements on the amount of the organic solvent used, as long as it is sufficient to allow the reaction to proceed smoothly. In this invention, the temperature of the enzymatic reaction is preferably 20-40°C, and the time is preferably 0.5-12 h, more preferably 2 h; the Antarctic Candida immobilized lipase selectively esterifies (R)-1-acetoxy-5-hydroxyhexane. In a specific embodiment of this invention, gas chromatography is preferably used for central control, and the reaction is immediately stopped once (S)-enantiomer products are detected in the reaction system; the chromatographic column of the gas chromatography is preferably a chiral cyclodextrin column.

[0042] After the enzymatic reaction is completed, the present invention preferably filters the resulting reaction solution with diatomaceous earth to remove the enzyme, concentrates the resulting filtrate by rotary evaporation, and distills the remaining product under reduced pressure to obtain (R)-6-acetoxyhexyl-2-ol butyrate. Unreacted (S)-1-acetoxy-5-hydroxyhexane is then reacted with dichloromethane, butyryl chloride, and pyridine to obtain (S)-6-acetoxyhexyl-2-ol butyrate.

[0043] In this invention, the preparation method of the racemic form of (R)-6-acetoxyhexyl-2-ol butyrate includes the following steps:

[0044] A fourth esterification reaction was carried out by mixing 1-acetoxy-5-hydroxyhexane, n-butyryl chloride, pyridine and an organic solvent to give 6-acetoxyhex-2-ol butyrate.

[0045] In this invention, the molar ratio of 1-acetoxy-5-hydroxyhexane, n-butyryl chloride and pyridine is preferably 1:1 to 1.5:1 to 1.5, more preferably 1:1.2:1.2; the solvent for the fourth esterification reaction is preferably a haloalkane, more preferably dichloromethane; the temperature of the fourth esterification reaction is preferably room temperature, and the time is preferably 0.5 to 12 h, more preferably 2 h.

[0046] After the fourth esterification reaction, the present invention preferably quenches the reaction with brine, extracts the resulting reaction solution with petroleum ether, washes and dries the organic layer, and concentrates it to obtain a crude product. The crude product is then subjected to column chromatography and distillation to obtain 6-acetoxyhexyl-2-ol butyrate. In the present invention, the washing agent is preferably a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is preferably 5 wt%; the drying agent is preferably anhydrous sodium sulfate; the eluent for column chromatography is preferably a mixed solvent of petroleum ether and diethyl ether, and the volume ratio of petroleum ether to diethyl ether is preferably 9:1.

[0047] In this invention, the preparation method of (R)-3-acetoxyhexyl butyrate includes the following steps:

[0048] (R)-3-hydroxybutyric acid, n-hexanol and an acidic catalyst were mixed and subjected to a second esterification reaction to obtain (R)-3-hydroxybutyrate hexyl ester;

[0049] The (R)-3-hydroxybutyrate hexyl ester, acetic anhydride and pyridine were mixed and subjected to a third esterification reaction to obtain (R)-3-acetoxybutyrate hexyl ester.

[0050] In this invention, the synthetic route for (R)-3-acetoxyhexyl butyrate is as follows:

[0051]

[0052] Wherein: (i) acidic catalyst / hexanol / dichloromethane; (ii) acetic anhydride / pyridine.

[0053] The preparation method of (R)-3-acetoxybutyrate hexyl ester is described in detail below with reference to the synthetic route.

[0054] This invention involves a second esterification reaction of (R)-3-hydroxybutyric acid, n-hexanol, and an acidic catalyst to obtain hexyl (R)-3-hydroxybutyrate. In this invention, the acidic catalyst is preferably concentrated sulfuric acid; the preferred molar ratio of (R)-3-hydroxybutyric acid to concentrated sulfuric acid is 1 mol: 1–3 mL, more preferably 1 mol: 2 mL; the preferred molar ratio of (R)-3-hydroxybutyric acid to n-hexanol is 1 mol: 500 mL; the esterification reaction preferably also includes a solvent, preferably dichloromethane; the preferred temperature for the esterification reaction is 100–150 °C, more preferably 120 °C, and the preferred time is 3–9 h, more preferably 6 h. After the esterification reaction is completed, this invention preferably adjusts the pH of the resulting reaction solution to 8 using a sodium carbonate solution, then separates the layers, and distills the resulting organic layer under reduced pressure to obtain hexyl (R)-3-acetoxybutyrate.

[0055] After obtaining (R)-3-acetoxybutyrate hexyl ester, the present invention mixes the (R)-3-hydroxybutyrate hexyl ester, acetic anhydride, and pyridine to carry out a third esterification reaction to obtain (R)-3-acetoxybutyrate hexyl ester. In the present invention, the molar ratio of (R)-3-hydroxybutyrate hexyl ester to acetic anhydride is preferably 8-12:10-15, more preferably 10:12; the molar ratio of (R)-3-acetoxybutyrate hexyl ester to pyridine is preferably 10 mmol:1-2 mL, more preferably 10 mmol:1.2 mL; the reaction temperature is preferably room temperature, and the reaction time is preferably 12-24 h. After the third esterification reaction is completed, the present invention preferably quenches the reaction with a 5 wt% hydrochloric acid aqueous solution, and then the obtained reaction solution is washed, dried, and rotary evaporated sequentially to obtain a crude product; the crude product is then subjected to column chromatography and vacuum distillation sequentially to obtain (R)-3-acetoxybutyrate hexyl ester. In this invention, the washing agent is preferably brine; the drying agent is preferably anhydrous magnesium sulfate; and the eluent for column chromatography is preferably a mixed solvent of petroleum ether and diethyl ether, wherein the volume ratio of petroleum ether to diethyl ether is preferably 9:1.

[0056] The present invention also provides a cinchona barbadensis lure, comprising a slow-release carrier and an active component loaded on the slow-release carrier, wherein the active component is the cinchona barbadensis sex pheromone described in the above scheme or the cinchona barbadensis sex pheromone prepared by the preparation method described in the above scheme.

[0057] In this invention, the material of the sustained-release carrier is preferably PVC, specifically a PVC plastic bottle or a PVC plastic tube. The height of the PVC plastic bottle is preferably 55±3 mm, the diameter is preferably 13±5 mm, and the thickness is preferably 0.25±0.2 mm. The length of the PVC plastic tube is preferably 8±2 cm, and the diameter is preferably 1–4 mm. Specifically, the active component is dissolved in a solvent, and then the active component solution is encapsulated in a PVC plastic bottle or PVC plastic tube. During use, the active component is slowly released along with the solvent.

[0058] In this invention, the loading amount of active components on a single cinchona barbadensis lure is preferably 2500–3500 μg, more preferably 2800–3000 μg. Specifically, the loading amount of the active components refers to the total amount of (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate.

[0059] The present invention also provides a method for preparing the cinchona horned bug lure described in the above-mentioned scheme, comprising the following steps:

[0060] The sex pheromone of the cinchona viper was loaded onto a sustained-release carrier to obtain a cinchona viper lure.

[0061] In this invention, the cinchona horn mirid bug sex pheromone is used after being dissolved; the solvent for dissolving is dichloromethane; in this invention, the total concentration of (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate in the active component solution obtained by dissolution is preferably 5 to 30 μg / μL, more preferably 5 to 10 μg / μL, and even more preferably 7.5 μg / μL.

[0062] In this invention, when the sustained-release carrier is a PVC plastic bottle, the preparation method of the lure specifically includes: dissolving the sex pheromone of the cinchona barbadensis in a solvent, adding the resulting solution dropwise into the PVC plastic bottle, and then sealing the bottle opening. The amount of solution added is preferably controlled according to the concentration of the active component in the solution and the loading of the active component in a single lure.

[0063] In this invention, when the sustained-release carrier is a PVC plastic tube, the preparation method of the lure specifically includes: dissolving the sex pheromone of the cinchona barbadensis in a solvent, injecting the resulting solution into the PVC plastic tube, and sealing both ends of the rubber tube. The injection volume of the solution is preferably controlled according to the concentration of the active component in the solution and the loading of the active component in a single lure.

[0064] This invention also provides the application of the cinchona horned bug sex pheromone or the cinchona horned bug lure described in the above-mentioned scheme in the control of cinchona horned bugs. In this invention, the lure is preferably used in the early stage of adult emergence of cinchona horned bugs. When applying it, it is preferred to use the lure in conjunction with a special boat-shaped trap, with a preferred density of 2-4 sets / acre. In a specific embodiment of this invention, it is preferred to fix the trap 10-20 cm above the top of the tea tree and clean the trap in a timely manner. The lure is preferably replaced every two months.

[0065] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0066] Example 1

[0067] Preparation of (R)-6-acetoxyhexyl-2-ol butyrate: Acetyl chloride (0.29 mL, 4.1 mmol), 1,5-hexanediol (0.472 g, 4 mmol), and N,N-diisopropylethylamine (1.39 mL, 8 mmol) were added to dichloromethane (8 mL). The reaction was stirred at -78 °C for 3 hours, then quenched with 10 mL of brine and extracted with diethyl ether (25 mL × 2). The combined ether layers were washed twice with brine, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain crude 1-acetoxy-5-hydroxyhexane (0.58 g) containing 1.1% 1,5-hexanediol diacetate and a small amount of 5-acetoxy-1-hexanol. Column chromatography separation (petroleum ether / diethyl ether = 6 / 4), followed by concentration and vacuum distillation (110℃ / 0.03mm Hg) to obtain 1-acetoxy-5-hydroxyhexane (0.52g, 82%), containing <0.5% 5-acetoxy-1-hexanol impurity.

[0068] 1-Acetoxy-5-hydroxyhexane (0.52 g, 3.3 mmol) was dissolved in diethyl ether (8 mL), vinyl butyrate (0.5 mL, 4 mmol) was added, and Candida antarcticis immobilized lipase (40 mg) was added. The mixture was stirred at high speed and the reaction was monitored by gas chromatography (chiral cyclodextrin column) to detect the product (R)-6-acetoxyhexyl-2-ol butyrate. The enzyme selectively esterified (R)-1-acetoxy-5-hydroxyhexane. The reaction was stopped immediately once the (S)-enantiomer was detected in the reaction system. The enzyme was removed by filtration with a small amount of diatomaceous earth, and the product was concentrated on a rotary evaporator. The residue was separated by column chromatography (petroleum ether / diethyl ether = 9 / 1). The product obtained from the column chromatography was then distilled under reduced pressure (125 °C / 0.04 mm Hg) to give 0.27 g of (R)-6-acetoxyhexyl-2-ol butyrate, with a yield of 72%. Unreacted (S)-1-acetoxy-5-hydroxyhexane was added to a dichloromethane solution, followed by the addition of butyryl chloride and pyridine. After reaction and purification, 0.29 g of (S)-6-acetoxyhex-2-ol butyrate was obtained, with a yield of 77%.

[0069] The enzymatic reaction was continued for 2 hours to give (R)-6-acetoxyhexyl-2-ol butyrate with a chiral purity of 96.2% (ee); (S)-6-acetoxyhexyl-2-ol butyrate had a chiral purity of 99.6% (ee). The enzymatic reaction was continued for 1.25 hours to give (R)-6-acetoxyhexyl-2-ol butyrate with a chiral purity of 98.6% (ee); (S)-6-acetoxyhexyl-2-ol butyrate had a chiral purity of 76.6% (ee). 1-Acetoxy-5-hydroxyhexane can be recycled to give the (S)-enantiomer with a higher ee.

[0070] The NMR identification data of (R)-6-acetoxyhexyl-2-ol butyrate are as follows:

[0071] 1 HNMR (CDCl) 3, 400MHz) δ4.92(hex,J=6.4Hz;1H),4.05(t,J=6.4Hz;2H),2.25(t,J=7.2,2H),2.05(s;3 H), 1.65 (m; 4H); 1.52 (m; 2H), 1.40 (m; 2H), 1.21 (d, J = 6.4Hz; 3H), 0.95 (t, J = 7.2Hz; 3H).

[0072] 13 C NMR (CDCl3, 100MHz) δ173.35,171.17,70.34,64.29,36.61,35.54,28.41,21.90,20.98,20.02,18.57,13.66.

[0073] Preparation of 6-acetoxyhexyl-2-ol butyrate (racemic mixture): 1-acetoxy-5-hydroxyhexane and 1.2 equivalents of pyridine were dissolved in dichloromethane at 0 °C, and 1.2 equivalents of n-butyryl chloride were added dropwise to convert to the corresponding butyrate ester. After stirring at room temperature for 2 h, the reaction was quenched with brine, and the mixture was extracted twice with petroleum ether. The combined organic layers were backwashed with 5% hydrochloric acid solution, dried over anhydrous sodium sulfate, and concentrated. The residue was separated by column chromatography (petroleum ether / diethyl ether = 9 / 1). The product obtained from the column chromatography was then distilled under reduced pressure (125 °C / 0.04 mm Hg) to give 6-acetoxyhexyl-2-ol butyrate ester in 90% yield.

[0074] Preparation of (R)-3-acetoxybutyrate hexyl ester: (R)-3-hydroxybutyric acid (104 g, 1 mol) was added to 500 mL of n-hexanol, followed by 2 mL of concentrated sulfuric acid. The mixture was stirred at 120 °C for 6 hours. The pH was adjusted to 8 by adding sodium carbonate aqueous solution, and the mixture was separated. The organic layer was distilled under reduced pressure (115 °C / 0.03 mm Hg) to obtain 169 g of (R)-3-hydroxybutyrate hexyl ester, with a yield of 90%.

[0075] (R)-3-hydroxybutyrate hexyl ester (1.88 g, 10 mmol) was reacted with acetic anhydride (1.2 mL, 12 mmol) and pyridine (1.2 mL) overnight at room temperature. The reaction was quenched with brine (20 mL), and the mixture was extracted twice with petroleum ether (25 mL × 2). The combined organic layers were washed once with 5% hydrochloric acid aqueous solution, twice with brine, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The residue was separated by column chromatography (petroleum ether / diethyl ether = 9 / 1), and the product was then distilled under reduced pressure (120 °C / 0.03 mm Hg) to give (R)-3-acetoxybutyrate hexyl ester (1.9 g, 83%).

[0076] The structural identification data for (R)-3-acetoxyhexyl butyrate are as follows:

[0077] 1 H NMR (CDCl) 3, 400MHz) δ5.27 (hex, J=6.4Hz; 1H), 4.08 (t, J=6.8Hz; 2H), 2.63 (dd, J=15.2, 7.2; 1H), 2.49 (dd, J=1 5.2, 5.6; 1H), 2.02 (s; 3H), 1.60 (m; 2H); 1.30 (m; 6H), 1.29 (d, J = 6.4Hz; 3H), 0.89 (t, J = 7.2Hz; 3H).

[0078] 13 C NMR (CDCl3, 100MHz) δ170.34,170.22,67.38,64.85,40.90,31.41,28.55,25.55,22.54,21.19,19.90,14.00.

[0079] Example 2

[0080] PVC plastic bottle core decoy method solution:

[0081] 1) Preparation of sustained-release carrier: PVC plastic bottles with a height of 55mm, a diameter of 13mm, and a thickness of 0.25mm were selected as the sustained-release carrier.

[0082] 2) Add (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate to dichloromethane at a mass ratio of 1:1, mix well, and obtain a solution with a total concentration of (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate of 7.5 μg / μL for later use.

[0083] 3) Preparation of the lure core

[0084] 400 μL of the sex attractant solution prepared in step 2) was injected into the sustained-release carrier prepared in step 1), and then the bottle was sealed to obtain the cinchona horned bug lure. The loading of active components in a single lure is 3000 μg, of which the contents of (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate are both 1500 μg.

[0085] Example 3

[0086] 1) Select a PVC plastic tube with a diameter of 2mm as the slow-release carrier.

[0087] 2) Dissolve (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate in chromatographically pure dichloromethane to obtain a solution with a total concentration of 7.5 μg / μl of (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate for later use.

[0088] 3) Inject 400 μl of the solution obtained in step 2) into the sustained-release carrier in step 1), and then seal both ends to obtain the pheromone attractant for cinchona barbadensis. The loading of active components in a single attractant is 3000 μg.

[0089] Example 4

[0090] The other conditions were the same as in Example 2, except that the ratio of (R)-6-acetoxyhexyl-2-ol butyrate to (R)-3-acetoxyhexyl butyrate was changed to 21:9. The resulting core contained 2100 μg of (R)-6-acetoxyhexyl-2-ol butyrate and 900 μg of (R)-3-acetoxyhexyl butyrate.

[0091] Example 5

[0092] The other conditions were the same as in Example 2, except that the ratio of (R)-6-acetoxyhexyl-2-ol butyrate to (R)-3-acetoxyhexyl butyrate was changed to 9:21. The resulting core contained 900 μg of (R)-6-acetoxyhexyl-2-ol butyrate and 2100 μg of (R)-3-acetoxyhexyl butyrate.

[0093] Comparative Example 1

[0094] The other conditions were the same as in Example 2, except that (R)-3-acetoxyhexyl butyrate was omitted, resulting in a core loaded with 3000 μg of (R)-6-acetoxyhexyl-2-ol butyrate.

[0095] Comparative Example 2

[0096] The other conditions were the same as in Example 2, except that (R)-6-acetoxyhexyl-2-ol butyrate was omitted, resulting in a core loaded with 3000 μg of (R)-3-acetoxyhexyl butyrate.

[0097] Application Example 1

[0098] The lures prepared in Examples 2, 4, 5, Comparative Example 1, and Comparative Example 2 were used in the trapping experiment in the application example. The trapping effect of lures with different proportions of active components was tested. The trapping experiment was conducted in a tea garden in Jiexi County, Jieyang City, Guangdong Province. The blank control was a PVC plastic bottle with added dichloromethane.

[0099] Sex pheromone was used in combination with boat-shaped traps, with each treatment repeated three times. The boat-shaped traps were randomly arranged in a checkerboard pattern in the tea garden, with each trap 5 cm above the tea trees and spaced 15 m apart. The number of insects trapped was counted daily for a total of 7 days. The data are listed in Table 1.

[0100] Table 1. Field trapping experiments using different proportions of sex pheromones from cinchona barbadensis.

[0101]

[0102] In Table 1, the letters following the numbers indicate that the data analyzed by the data analysis software showed significant differences. The same letter indicates no significant difference, while different letters indicate significant differences.

[0103] As can be seen from the data in Table 1, the attraction activity of the sex pheromone of the cinchona barbadensis varies with different ratios. The best attraction effect is achieved when the ratio of (R)-6-acetoxyhexyl-2-ol butyrate to (R)-3-acetoxyhexyl butyrate is 1:1, which is significantly better than other ratio combinations.

[0104] Application Example 2

[0105] The trapping effect of different sized traps was tested in a tea garden in Jiexi County, Jieyang City, Guangdong Province. The lure cores used were those prepared in Example 2, with an active component loading of 3000 μg and a mass ratio of (R)-6-acetoxyhexyl-2-ol butyrate to (R)-3-acetoxyhexyl butyrate of 1:1. Sex pheromones were used in conjunction with boat-shaped traps, with each treatment replicated four times. Two sizes of boat-shaped traps were randomly arranged in a checkerboard pattern in the tea garden, each trap 5 cm above the tea trees, with a 15 m interval between traps. The average values ​​of the collected data are shown in Table 2.

[0106] Table 2 Field trapping experiment of cinchona horned bug using boat-shaped traps of different sizes.

[0107]

[0108] As can be seen from the data in Table 2, the trapping efficiency of the cinchona barb sex pheromone combined with boat-shaped traps of different sizes varies significantly, with large boat-shaped traps showing significantly better trapping efficiency than small boat-shaped traps.

[0109] Application Example 3

[0110] The trapping effect of traps at different heights was tested in a tea garden in Jiexi County, Jieyang City, Guangdong Province. The lures used were those prepared in Example 2, with an active component loading of 3000 μg and a mass ratio of (R)-6-acetoxyhexyl-2-ol butyrate to (R)-3-acetoxyhexyl butyrate of 1:1. The lures were used in conjunction with boat-shaped traps, with each treatment replicated four times. The boat-shaped traps were randomly arranged in a checkerboard pattern in the tea garden, with three treatments: traps 20 cm, 10 cm, and 5 cm above the tea trees, spaced 15 m apart. The average values ​​of the collected data are listed in Table 3.

[0111] Table 3 Field trapping experiments of cinchona leaf bugs at different operating heights.

[0112] 20 15.67±0.11c 10 41.67±3.67b 5 72.01±5.45a

[0113] The different letters following the numbers in Table 3 represent significant differences in the data analyzed by data analysis software.

[0114] As can be seen from the data in Table 3, the attraction activity of the traps varied at different heights, with the best attraction effect observed when the traps were 5cm above the tea trees, significantly better than other ratio combinations.

[0115] Application Example 4

[0116] This embodiment compares the attraction of female cinchona barbadensis bug lures with that of female cinchona barbadensis bugs in a tea garden in Jiexi County, Jieyang City, Guangdong Province. All lures used were prepared in Example 2, with a mass ratio of (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate of 1:1. The sex pheromone dosage was 3000 μg / lure, and the lures were used in conjunction with a boat-shaped trap. The control group consisted of female cinchona barbadensis bugs collected from the tea garden. The blank control was a PVC plastic bottle containing dichloromethane.

[0117] Boat-shaped insect traps were randomly arranged in a checkerboard pattern in the tea garden. Each treatment was repeated three times. Each trap was 10 cm above the tea tree and spaced 20 m apart. The number of insects trapped was counted daily for a total of 7 days. The results are shown in Table 4.

[0118] Table 4. Comparison of the attraction effects of sex pheromones and female cinchona leaf bugs on cinchona leaf bugs.

[0119] Cinchona horned bug sex pheromone 93.67±9.82a Female cinchona mirid bug 20.00±2.00b Blank control 0.33±0.33b

[0120] The different letters following the data in Table 4 indicate that the data analyzed by the data analysis software showed significant differences.

[0121] As can be seen from the survey data in Table 4, both the cinchona horned bug lure and the female cinchona horned bug of this invention can successfully attract male cinchona horned bugs, with the lure being more effective than the female. While female cinchona horned bugs can attract males within a certain distance, the lure of this invention, due to its higher sex pheromone content compared to the female, can attract even more males.

[0122] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A cinchona migraine sex pheromone, composed of (R)-6-acetoxyhexyl-2-ol butyrate and (R)-3-acetoxyhexyl butyrate; wherein the mass ratio of (R)-6-acetoxyhexyl-2-ol butyrate to (R)-3-acetoxyhexyl butyrate is (1~10):(1~2).

2. The method for preparing the cinchona horned mirid bug sex pheromone according to claim 1, characterized in that, The preparation method of the (R)-6-acetoxyhexyl-2-ol butyrate includes the following steps: Acetyl chloride, 1,5-hexanediol, N,N-diisopropylethylamine and an organic solvent were mixed and subjected to a first esterification reaction to give 1-acetoxy-5-hydroxyhexane; The 1-acetoxy-5-hydroxyhexane, vinyl butyrate, Candida antarcticis immobilized lipase and organic solvent were mixed and subjected to an enzymatic reaction to obtain (R)-6-acetoxyhex-2-ol butyrate. The preparation method of (R)-3-acetoxybutyrate hexyl ester includes the following steps: (R)-3-hydroxybutyric acid, n-hexanol and an acidic catalyst were mixed and subjected to a second esterification reaction to obtain (R)-3-hydroxybutyrate hexyl ester; The (R)-3-hydroxybutyrate hexyl ester, acetic anhydride and pyridine were mixed and subjected to a third esterification reaction to obtain (R)-3-acetoxybutyrate hexyl ester.

3. A lure for the cinchona horned bug, characterized in that, The product includes a sustained-release carrier and an active component loaded on the sustained-release carrier. The active component is the cinchona barbadensis sex pheromone of claim 1 or the cinchona barbadensis sex pheromone prepared by the preparation method of claim 2. The loading amount of the active component on a single cinchona barbadensis lure is 2500~3500 μg.

4. The cinchona horned bug lure according to claim 3, characterized in that, The sustained-release carrier is made of PVC.

5. The method for preparing the cinchona horned bug lure according to any one of claims 3 to 4, characterized in that, Includes the following steps: The sex pheromone of the cinchona viper was loaded onto a sustained-release carrier to obtain a cinchona viper lure.

6. The preparation method according to claim 5, characterized in that, The cinchona horned bug sex pheromone is used after being dissolved; the solvent used for dissolution is dichloromethane.

7. The application of the cinchona horn mirid bug sex pheromone as described in claim 1 or the cinchona horn mirid bug lure as described in any one of claims 3 to 4 in the control of cinchona horn mirid bugs.

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