Application of soapberry in preparation of insect pheromone

Abstract

This invention discloses the application of Sapindus mukorossi in the preparation of insect pheromones, belonging to the field of insect pheromone synthesis. The preparation method is simple, the raw materials are abundant, and the cost is low. This invention uses Sapindus mukorossi as raw material, extracting Sapindus mukorossi oil. The Sapindus mukorossi oil is directly reduced to obtain mixed fatty alcohols, which are then subjected to olefin metathesis and molecular distillation to obtain high-purity cis-9-tetradecenol and cis-11-hexadecenol. Cis-9-tetradecenol and cis-11-hexadecenol are then subjected to oxidation or acetylation reactions to obtain cis-9-tetradecenal, cis-11-hexadecenal, cis-9-tetradecenol acetate, and cis-11-hexadecenol acetate.

Description

Technical Field

[0001] This invention belongs to the field of insect pheromone synthesis, specifically involving the application of Sapindus mukorossi in the preparation of insect pheromones. Background Technology

[0002] Soapberry (Sapindus mulorossi Gaertn.), also known as soap tree or hand soap fruit, is a deciduous tree belonging to the Sapindaceae family and the Sapindus genus, distributed throughout Southeast Asia. The aril of the soapberry is rich in saponins, possessing excellent foaming and detergency properties. It can be used as a natural active ingredient in shampoos, shampoos, and various skincare cosmetics, and also has antibacterial and antipruritic effects. Soapberry saponins are also excellent pesticide emulsifiers, showing good killing effects against cotton aphids, spider mites, and sweet potato weevils. The soapberry kernel contains abundant plant oil, with an oil content exceeding 40%. The oil mainly contains various fatty acids, with unsaturated fatty acids accounting for over 80%, including a relatively high content of oleic acid (around 50%), cis-11-eicosenoic acid (around 25%), and linoleic acid (around 10%). Soapberry oil has a wide range of industrial applications, such as being used as a lubricant in the machinery industry, softening and destaticating wool in the textile industry, acting as a blending agent in the ink industry, and making soaps and hand soaps in the chemical industry.

[0003] Insect pheromones are a collective term for trace chemical substances that facilitate chemical communication between organisms. They are compounds used by insects to express various information such as gathering, foraging, mating, and alertness; they are the chemical molecular language of insect communication. For example, in nature, female adult pests release a compound called a sex pheromone after reaching sexual maturity. Released into the air, it diffuses with the airflow, stimulating the chemical sensory organs in the antennae of male insects, causing male sexual impulses and attracting them to fly towards the release source to mate with the releasing female adult for reproduction. At the same time, as a chemical communication tool during the reproductive stage between insects of the same species, the highly complex and unique chemical structure of insect sex pheromones is an important guarantee for reproductive isolation between insect species. Therefore, sex pheromones from different insects cannot be substituted for each other and will not cause confusion. They have significant practical value in regional insect surveys, plant quarantine, and green pest control.

[0004] Studies have shown that cis-9-tetradecenol is a sex pheromone component of the beet armyworm and apple leafroller; cis-9-tetradecenol acetate is a sex pheromone component of the fall armyworm and diamondback moth; cis-9-tetradecenal is a sex pheromone component of the bindweed moth and cotton bollworm; cis-11-hexadecenol is a sex pheromone component of the two-spotted stem borer, oriental armyworm, and diamondback moth; cis-11-hexadecenol acetate is a sex pheromone component of the sugarcane stem borer; and cis-11-hexadecenal is a sex pheromone component of the rice stem borer, cotton bollworm, tobacco budworm, diamondback moth, pine shoot borer, three-spotted stem borer, large stem borer, European sunflower leaf borer, corn armyworm, and boxwood leafminer.

[0005] There are several existing methods for preparing 9Z-tetradecenol and 11Z-hexadecenol, differing mainly in the method of constructing the cis double bond in the molecule. The simplest method is to construct the cis double bond through olefin metathesis. The preparation of 9Z-tetradecenol and 11Z-hexadecenol via olefin metathesis requires two raw materials: 9-octadecenol and 11-eicosenool. 11-eicosenool is in short supply in the market, and the current method for its preparation uses jojoba oil as a raw material. Jojoba oil has excellent properties, wide applications, and a high market price, but domestic production is very small, leading to large-scale imports. Therefore, it is necessary to find a suitable, abundant, and inexpensive raw material for the preparation of 11-eicosenool. Summary of the Invention

[0006] Purpose of the invention: In order to overcome the shortcomings of the existing technology, the present invention provides the application of Sapindus mukorossi in the preparation of insect pheromones.

[0007] Technical solution: To achieve the above objectives, the present invention adopts the following technical solution:

[0008] The application of Sapindus mukorossi in the preparation of insect pheromones involves the following steps: Sapindus mukorossi is used as a raw material to prepare various insect pheromones.

[0009] (1) Using Sapindus mukorossi as raw material, extract Sapindus mukorossi oil from Sapindus mukorossi;

[0010] (2) Reduce Sapindus mukorossi oil to obtain mixed fatty alcohols;

[0011]

[0012] (3) After the mixed fatty alcohols and 1-hexene undergo olefin metathesis, high-purity cis-9-tetradecenol and cis-11-hexadecenol are obtained by molecular distillation.

[0013]

[0014] (4) Oxidation or acetylation of cis-9-tetradecenol yields cis-9-tetradecenal and cis-9-tetradecenol acetate.

[0015]

[0016] (5) Oxidation or acetylation of cis-11-hexadecenol yields cis-11-hexadecenal and cis-11-hexadecenol acetate.

[0017]

[0018] Beneficial effects: This invention provides the application of Sapindus mukorossi in the preparation of insect pheromones, which has the following advantages compared with the prior art: There is no research on the preparation of insect pheromones using Sapindus mukorossi as raw material, and this invention fills the gap in this field; Sapindus mukorossi kernels are rich in 50%-60% oleic acid and 20%-30% cis-11-eicosenoic acid, and various insect pheromones can be prepared by extracting Sapindus mukorossi oil. The preparation method is simple, the raw material source is sufficient and the cost is low, and it provides a new use for Sapindus mukorossi, which can avoid the waste of Sapindus mukorossi. Attached Figure Description

[0019] Figure 1 This is a reaction flow diagram of the present invention. Detailed Implementation

[0020] The invention will now be further described with reference to the accompanying drawings.

[0021] As attached Figure 1 As shown, the application of Sapindus mukorossi in the preparation of insect pheromones involves the following steps: Sapindus mukorossi is used as a raw material to prepare various insect pheromones.

[0022] 1. Extraction of Sapindus mukorossi oil:

[0023] (1) Dry the Sapindus mukorossi seeds, crack open the seed coat to remove the kernel, crush them and dry them for later use;

[0024] (2) Weigh 100g of Sapindus mukorossi seed kernel powder (material-liquid ratio 1:20), place it in a Soxhlet extractor, add petroleum ether (or n-hexane), heat and reflux at 90℃ for 8h, filter, remove solvent by vacuum distillation, and obtain 42.8g of pale yellow Sapindus mukorossi oil, yield 42.8%.

[0025] 2. Preparation of Sapindus mukorossi oil mixed with fatty alcohols:

[0026] 60g of Sapindus mukorossi oil was mixed with 200ml of tetrahydrofuran, and 34.6ml of red aluminum solution was added dropwise at 45℃ under nitrogen protection. After the addition was complete, the reaction was carried out for 5 hours. Saturated sodium sulfite was added to quench the reaction, and the mixture was filtered and extracted with dichloromethane to obtain 17.6g of Sapindus mukorossi oil mixed with fatty alcohols, with a yield of 78.9%.

[0027] 3. Preparation of cis-9-tetradecenoic acid and cis-11-hexadecenoic acid:

[0028] 134g of Sapindus mukorossi oil mixed with fatty alcohols, 100ml of 1-hexene, and 100ml of tetrahydrofuran were mixed, and 5.1g of a cis-selective olefin metathesis catalyst was added under nitrogen protection. The reaction was carried out at room temperature (or 25℃) for 5 hours. The reaction was quenched with ethanol, and the low-boiling solvent was removed by vacuum distillation. Then, a mixed alcohol mainly composed of cis-9-tetradecenol and cis-11-hexadecenol was obtained by ordinary distillation. Finally, the mixed alcohol was added to a molecular distillation apparatus, evacuated to 0.3mmHg, and slowly heated. After high-vacuum molecular distillation, 63.2g of cis-9-tetradecenol (yield 85.0%, purity 95.2%) was collected at 128-130℃, and 30.8g of cis-11-hexadecenol (yield 85.6%, purity 93.6%) was collected at 134-136℃. 4. Preparation of cis-9-tetradecenol:

[0029] At 0 °C, 3.86 g (12 mmol) of iodophenyl diacetic acid (BAIB) was added to a 10 mL solution of 2.12 g (10 mmol) of cis-9-tetradecenoic acid and 0.16 g (1 mmol) of 2,2,6,6-tetramethylpiperidine oxide TEMPO (TEMPO). The mixture was then brought to room temperature and reacted for 1 h. The mixture was extracted, rotary evaporated under reduced pressure, and purified by column chromatography to obtain 1.94 g of cis-9-tetradecenoic acid, with a yield of 92.4%.

[0030] 5. Preparation of cis-11-hexadecenal:

[0031] At 0 °C, 3.86 g (12 mmol) of iodophenyl diacetic acid (BAIB) was added to a 10 mL solution of 2.40 g (10 mmol) of cis-11-hexadecenol and 0.16 g (1 mmol) of 2,2,6,6-tetramethylpiperidine oxide TEMPO (TEMPO). The mixture was stirred and brought to room temperature. After 1 h, the mixture was extracted, evaporated under reduced pressure, and purified by column chromatography to obtain 2.21 g of cis-11-hexadecenol, with a yield of 92.8%.

[0032] 6. Preparation of cis-9-tetradecenoic acid acetate:

[0033] In a three-necked flask, 2.12 g (10 mmol) of cis-9-tetradecenol, 1.22 g (12 mmol) of acetic anhydride, 10 mL of dichloromethane, and 0.08 g (1 mmol, 10 mol%) of pyridine were added sequentially, and the mixture was reacted at room temperature for 3 h. The mixture was then extracted, rotary evaporated under reduced pressure, and purified by column chromatography to obtain 2.30 g of cis-9-tetradecenol acetate, with a yield of 90.6%.

[0034] 7. Preparation of cis-11-hexadecenol acetate:

[0035] In a three-necked flask, 2.40 g (10 mmol) of cis-11-hexadecenol, 1.22 g (12 mmol) of acetic anhydride, 10 mL of dichloromethane, and 0.08 g (1 mmol, 10 mol%) of pyridine were added sequentially, and the mixture was reacted at room temperature for 3 h. The mixture was then extracted, rotary evaporated under reduced pressure, and purified by column chromatography to obtain 2.54 g of the product cis-11-hexadecenol acetate, with a yield of 90.0%.

[0036] 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. The use of Sapindus in the preparation of insect pheromones, characterized in that, The application relates to preparation of various insect pheromones from soapberry, including the following steps: (1) taking soapberry as raw material, soapberry oil is extracted from soapberry; (2) reducing the soapberry oil to obtain mixed fatty alcohols; (3) after olefin metathesis of the mixed fatty alcohols and 1-hexene, olefinic alcohols are obtained through molecular distillation; (4) oxidizing or acetylating the olefinic alcohols to obtain olefinic aldehydes or olefinic alcohol acetates; The insect pheromones are cis-9-tetradecenyl alcohol, cis-9-tetradecenyl alcohol acetate, cis-9-tetradecenal, cis-11-hexadecenyl alcohol, cis-11-hexadecenyl alcohol acetate and cis-11-hexadecenal.

2. The use of Sapindus saponin according to claim 1 in the preparation of an insect pheromone, characterized in that, The preparation process of the fatty alcohols is as follows: 60g of soapberry oil is mixed with 200ml of tetrahydrofuran, then 34.6ml of red aluminum solution is added dropwise under nitrogen protection at 45 DEG C, the reaction is carried out for 5h after dropwise addition, saturated sodium sulfite is added for quenching, filtration is conducted, dichloromethane is used for extraction, and oil-like soapberry oil mixed fatty alcohols are obtained.

3. The use of Sapindus saponin according to claim 1 in the preparation of insect pheromones, characterized in that, The preparation process of the cis-9-tetradecenyl alcohol and cis-11-hexadecenyl alcohol is as follows: 134g of soapberry oil mixed fatty alcohols, 100ml of 1-hexene and 100ml of tetrahydrofuran are mixed, then 5.1g of cis-selective olefin metathesis catalyst is added under nitrogen protection, the reaction is carried out for 5h at room temperature, ethanol is added for quenching, low-boiling-point solvents are removed, and high-purity cis-9-tetradecenyl alcohol and cis-11-hexadecenyl alcohol are obtained through ordinary rectification and molecular rectification.

4. The use of Sapindus according to claim 1 or 3 for the preparation of an insect pheromone, characterized in that, The preparation process of the cis-9-tetradecenal is as follows: 12mmol of iodobenzene diacetic acid is added to a 10ml dichloromethane solution containing 10mmol of cis-9-tetradecenyl alcohol and 1mmol of 2,2,6,6-tetramethylpiperidine oxide TEMPO at 0 DEG C, then the temperature is increased to room temperature, the reaction is carried out for 1h, and cis-9-tetradecenal is obtained after treatment and purification.

5. The use of Sapindus according to claim 1 or 3 for the preparation of an insect pheromone, characterized in that, The preparation process of the cis-11-hexadecenal is as follows: 12mmol of iodobenzene diacetic acid is added to a 10ml dichloromethane solution containing 10mmol of cis-11-hexadecenyl alcohol and 1mmol of 2,2,6,6-tetramethylpiperidine oxide TEMPO at 0 DEG C, the temperature is increased to room temperature under stirring, the reaction is carried out for 1h, and cis-11-hexadecenal is obtained after treatment and purification.

6. The use of Sapindus according to claim 1 or 3 for the preparation of an insect pheromone, characterized in that, The preparation process of the cis-9-tetradecenyl alcohol acetate is as follows: 10mmol of cis-9-tetradecenyl alcohol, 12mmol of acetic anhydride, 10ml of dichloromethane and 1mmol of pyridine are sequentially added to a reaction container, the reaction is carried out for 3h at room temperature, and cis-9-tetradecenyl alcohol acetate is obtained after treatment and purification.

7. The use of Sapindus according to claim 1 or 3 for the preparation of an insect pheromone, characterized in that, The preparation process of the cis-11-hexadecenyl alcohol acetate is as follows: 10mmol of cis-11-hexadecenyl alcohol, 12mmol of acetic anhydride, 10ml of dichloromethane and 1mmol of pyridine are sequentially added to a reaction container, the reaction is carried out for 3h at room temperature, and cis-11-hexadecenyl alcohol acetate is obtained after treatment and purification.

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