A method for preparing the codling moth pheromone (Z / E)-8-dodecen-1-ol acetate

Abstract

The application discloses a preparation method of a pear fruit borer pheromone (Z / E)-8-dodecene-1-ol acetate. Specifically, (Z / E)-8-dodecene-1-ol acetate is prepared in a high yield through the following steps of taking 1,8-octanedioic acid as a raw material, reduction, aldehyde group monoprotection, condensation, ring phosphate ester formation, olefin formation, deprotection, reduction and acetylation. The preparation method is simple and easy to implement, raw materials are easy to obtain, reaction selectivity is good, the proportion of (Z / E)-8-dodecene-1-ol acetate reaches 95:5, and the method is suitable for large-scale production.

Description

Technical Field

[0001] This invention belongs to the field of green biological pesticide technology, specifically relating to a method for preparing the pheromone (Z / E)-8-dodecene-1-ol acetate of the pear fruit moth. Background Technology

[0002] (Z / E)-8-dodecene-1-ol acetate is the main active ingredient in the pheromone of the pear fruit moth. It possesses advantages such as good attraction to the pear fruit moth, high specificity, and no harm to natural enemies, making it a high-quality biological pesticide that is increasingly valued and used. Studies have found that its biological activity is optimal when the molar ratio of (Z / E)-8-dodecene-1-ol acetate is 95:5.

[0003] In 1973, Holan G first synthesized an alkyne-containing intermediate using 1-iodo-6-chlorohexane and n-propylacetylene, and then prepared (Z / E)-8-dodecene-1-ol acetate by reduction with borane. Several institutions, including the Beijing Institute of Zoology, Chinese Academy of Sciences, improved this synthetic method, but it still suffered from the drawback of the difficulty in obtaining long-chain terminal alkyne raw materials. In 1985, Schaub B et al. proposed a more classic synthetic method for preparing (Z / E)-8-dodecene-1-ol acetate via the Wittig reaction of quaternary phosphate salts and aldehydes, which attracted attention from peers. However, this method had the disadvantage that the sulfur byproduct produced by using sodium DMSO as a base was difficult to remove completely and was prone to residue. In summary, the existing synthetic methods for (Z / E)-8-dodecene-1-ol acetate suffer from disadvantages such as the difficulty in obtaining raw materials, long reaction steps, harsh reaction conditions, and low yield. Further development of new preparation methods with shorter reaction steps, lower costs, and higher quality is needed. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing pear fruit moth pheromone (Z / E)-8-dodecene-1-ol acetate. This preparation method uses inexpensive raw materials, has a short reaction step, mild reaction conditions, is easy to operate, has a high yield, good reaction selectivity, and the ratio of cis to trans isomers of the product reaches 95:5, which can be used directly, omitting the separation and remixing steps of cis and trans isomers.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is: a method for preparing pear fruit moth pheromone (Z / E)-8-dodecene-1-ol acetate, the preparation method comprising the following steps:

[0006] (1) 1,8-Octaic acid reacts with SOCl2 to give the corresponding acyl chloride (I); (2) 5% Pd-BaSO4 was suspended in dry THF, 2,6-dimethylpyridine was added, the mixture was stirred, hydrogen gas was passed through to a certain pressure, acyl chloride (I) was added, and the mixture was reacted at 25-30℃ to obtain intermediate (II). No purification treatment was required, and it was directly used in the next step of the reaction. (3) Add ethylene glycol to toluene. p -TsOH and intermediate (II) were refluxed to separate water, yielding intermediate (III); (4) Under N2 atmosphere, zinc powder was suspended in THF, intermediate (III) was added, cooled to -5-10℃, and a THF solution of n-butyraldehyde and TiCl4 was slowly added. The reaction was carried out at 0℃, and after post-treatment, intermediate (IV) was obtained. (5) Intermediate (IV) is dissolved in THF, and n-BuLi, HMAP and N,N -Dimethylaminophosphoryl dichloride, reacted at room temperature, to give intermediate (V), which can be used directly in the next reaction without purification; (6) Intermediate (V) is dissolved in n-hexane and reacted in Li / NH3 (liq.) to prepare intermediate (VI); (7) Intermediate (VI) is added to H2O / THF, then TFA is added, and the reaction is carried out at room temperature to obtain intermediate (VII). (8) Intermediate (VII) is dissolved in ethanol, 10% Pd-C is added, hydrogen is passed through at room temperature for reduction, the mixture is filtered, the filtrate is evaporated under reduced pressure, and the residue is reacted with acetic anhydride and triethylamine (or pyridine) to obtain (Z / E)-8-dodecene-1-ol acetate.

[0007] As a preferred embodiment of the preparation method of the present invention, the specific operation of step (1) is as follows: 1,8-octanedioic acid is mixed with 2 times the amount of SOCl2. ， The reaction was refluxed for 1.5-2 hours, and excess SOCl2 was distilled off under reduced pressure to obtain acyl chloride (I).

[0008] As a preferred embodiment of the preparation method of the present invention, the specific operation of step (2) is as follows: a certain mass fraction of 5% Pd-BaSO4 is suspended in dry THF, 2,6-dimethylpyridine is added, stirred, hydrogen gas is passed through to 1-2 atm, acyl chloride (I) is added, reacted at 25-30℃ for 1-2 h, filtered, THF is distilled off under reduced pressure, n-hexane is added, filtered, concentrated, and intermediate (II) is obtained. It does not require purification treatment and is directly used in the next reaction.

[0009] In a preferred embodiment of the preparation method of the present invention, step (3) specifically involves adding 6-10% by mass of [unspecified ingredient] to toluene. p-TsOH, stir, then add ethylene glycol and intermediate (II), reflux to remove water for 5-6 hours, remove toluene by vacuum distillation, purify, and obtain intermediate (III).

[0010] As a preferred embodiment of the preparation method described in this invention, the specific operation of step (4) is as follows: under N2 atmosphere, zinc powder is suspended in THF, intermediate (III) is added, stirred, cooled to -5 to -10°C, n-butyraldehyde and TiCl4 / THF solution are slowly added, stirred for 20 min, heated to 0°C, reacted for 2 to 2.5 h, 10% K2CO3 solution is added, stirred, THF is removed by vacuum distillation, extracted with dichloromethane, dried with anhydrous sodium sulfate, filtered, concentrated, purified, and intermediate (IV) is obtained.

[0011] As a preferred embodiment of the preparation method of the present invention, the specific operation of step (5) is as follows: at 0°C, the THF solution of intermediate (IV) is added to the n-BuLi / n-hexane solution, stirred for 5 min, and then HMAP and N,N A THF solution of dimethylaminophosphoryl dichloride was stirred for 30 minutes, brought to room temperature, and reacted overnight. The THF was then distilled off under reduced pressure, water was added, and the mixture was extracted with dichloromethane to obtain intermediate (V). This intermediate was used directly in the next reaction without further purification.

[0012] As a preferred embodiment of the preparation method of the present invention, the specific operation of step (6) is as follows: add the n-hexane solution of intermediate (V) to the Li / NH3 (L) solution, react at room temperature for 15-30 min, add solid ammonium chloride, distill off ammonia, extract with n-hexane, separate and purify by silica gel column chromatography, and obtain intermediate (VI).

[0013] As a preferred embodiment of the preparation method described in this invention, the specific operation of step (7) is as follows: add intermediate (VI) to H2O / THF (volume ratio 1:8), stir, then add TFA, react at room temperature for 1 h, remove THF by vacuum distillation, add appropriate amount of water to the residue, extract with n-hexane, dry, concentrate, and obtain intermediate (VII), which is directly used in the next reaction.

[0014] As a preferred embodiment of the preparation method of the present invention, the specific operation of step (8) is as follows: intermediate (VII) is dissolved in ethanol, 10% Pd-C is added, hydrogen is introduced at room temperature, the reaction is carried out for 2 hours, filtered, the filtrate is evaporated under reduced pressure, the residue is added to acetic anhydride and triethylamine (or pyridine), the reaction is carried out at 8-11℃ for 3 hours, water is added, hexane is extracted, dried, concentrated, purified, and (Z / E) 8-dodecene-1-ol acetate is obtained.

[0015] In a preferred embodiment of the preparation method described in this invention, in step (2), the molar ratio of acyl chloride (I) to 2,6-dimethylpyridine is 1:2-2.2, and the mass fraction of 5% Pd-BaSO4 is 10%; in step (3), the molar ratio of intermediate (II) to ethylene glycol is 1:1; in step (4), the molar ratio of intermediate (III) to n-butyraldehyde, zinc powder, and TiCl4 is 1:1-1.2:3-3.3:1.3-1.5; in step (5), the molar ratio of intermediate (IV) to n-BuLi, N,N The molar ratio of dimethylaminophosphoryl dichloride is 1:2.2-2.5:2.2-2.5, and the volume ratio of THF to HMPA is 5-6:1; in step (6), the molar ratio of intermediate (V) to Li is 1:5-6, and the Li / NH3(L) is 1 / 8-9 (g / mL); in step (7), the molar ratio of intermediate (VI) to TFA is 1:1; in step (8), the molar ratio of intermediate (VII) to Ac2O, Et3N (or pyridine) is 1:1-1.1:1-1.1.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention develops a new preparation method for the pheromone (Z / E)-8-dodecene-1-ol acetate of the pear fruit moth. The raw materials used in this method are readily available and inexpensive, the reaction conditions are mild, it is easy to operate, the yield is high, the reaction selectivity is good, and the cis-trans ratio of the product isomers is 95:5, which can be used directly. The separation and remixing of cis-trans isomers are omitted, resulting in less environmental pollution and making it suitable for industrial production. Implementation

[0017] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the scope of protection of the present invention is not limited thereto. Example 1

[0018] Mix 10.4 g (0.1 mol) of 1,8-octanedioic acid with twice the amount of SOCl2. ， The reaction was refluxed for 1.5-2 hours, and excess SOCl2 was distilled off under reduced pressure to obtain acyl chloride (I). Example 2

[0019] 3.5 g of 5% Pd-BaSO4 was suspended in 400 mL of dry THF. 21.4 g (0.2 mol) of 2,6-dimethylpyridine was added, and the mixture was stirred. Hydrogen gas was passed through the mixture at normal pressure, and 14.1 g (0.1 mol) of acyl chloride (I) was added. The mixture was reacted at 30 °C for 2 h. After filtration, THF was distilled off under reduced pressure. Hexane was added, and the mixture was filtered and concentrated to obtain intermediate (II). This intermediate was used directly in the next reaction without further purification. Example 3

[0020] 3.7 g of 5% Pd-BaSO4 was suspended in 400 mL of dry THF. 23.5 g (0.22 mol) of 2,6-dimethylpyridine was added, the mixture was stirred, and hydrogen gas was passed through to 2 atm. 14.1 g (0.1 mol) of acyl chloride (I) was added, and the mixture was reacted at 25 °C for 1 h. The mixture was filtered, THF was distilled off under reduced pressure, n-hexane was added, the mixture was filtered, and the mixture was concentrated to obtain intermediate (II). This intermediate was used directly in the next reaction without further purification. Example 4

[0021] Add 6% by mass to 50 mL of toluene p -TsOH, stir, then add 6.2 g (0.1 mol) ethylene glycol and 7.2 g (0.1 mol) intermediate (II), reflux to remove water for 6 h, remove toluene by vacuum distillation, purify to obtain intermediate (III), yield 94.7%. Example 5

[0022] Add 10% by mass to 50 mL of toluene p -TsOH, stir, then add 6.2 g (0.1 mol) ethylene glycol and 7.2 g (0.1 mol) intermediate (II), reflux to remove water for 5 h, remove toluene by vacuum distillation, purify to obtain intermediate (III), yield 96.6%. Example 6

[0023] Under a nitrogen atmosphere, 19.5 g (0.3 mol) of zinc powder was suspended in 200 mL of THF, and 11.6 g (0.1 mol) of intermediate (III) was added. The mixture was stirred and cooled to -5 °C. A solution of 7.2 g (0.1 mol) of n-butyraldehyde and 28.3 g (0.15 mol) of TiCl4 / 100 mL of THF was slowly added. The mixture was stirred for 20 min, heated to 0 °C, and reacted for 2 h. A 10% K2CO3 solution was added, and the mixture was stirred. THF was removed by vacuum distillation, and the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, concentrated, and purified to obtain intermediate (IV) with a yield of 94.2%. Example 7

[0024] Under a nitrogen atmosphere, 21.5 g (0.33 mol) of zinc powder was suspended in 200 mL of THF, and 11.6 g (0.1 mol) of intermediate (III) was added. The mixture was stirred and cooled to -8 °C. A solution of 8.6 g (0.12 mol) of n-butyraldehyde and 24.5 g (0.13 mol) of TiCl4 / 80 mL of THF was slowly added. The mixture was stirred for 20 min, heated to 0 °C, and reacted for 2.5 h. A 10% K2CO3 solution was added, and the mixture was stirred. THF was removed by vacuum distillation, and the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, concentrated, and purified to obtain intermediate (IV) with a yield of 95.4%. Example 8

[0025] Under a nitrogen atmosphere, 20.2 g (0.31 mol) of zinc powder was suspended in 200 mL of THF, and 11.6 g (0.1 mol) of intermediate (III) was added. The mixture was stirred and cooled to -10 °C. A solution of 7.9 g (0.11 mol) of n-butyraldehyde and 26.4 g (0.14 mol) of TiCl4 / 100 mL of THF was slowly added. The mixture was stirred for 20 min, heated to 0 °C, and reacted for 2 h. A 10% K2CO3 solution was added, and the mixture was stirred. THF was removed by vacuum distillation, and the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, concentrated, and purified to obtain intermediate (IV) with a yield of 95.3%. Example 9

[0026] At 0℃, 250 mL of a THF solution containing 26.0 g (0.1 mol) of intermediate (IV) was added to 120 mL of a 2.1 M n-BuLi / n-hexane solution and stirred for 5 min. Then, 50 mL of HMAP and 35.4 g (0.25 mol) of HMAP were added. N,N 50 mL of dimethylaminophosphoryl dichloride THF solution was stirred for 30 min, brought to room temperature, and reacted overnight. The THF was removed by vacuum distillation, water was added, and the mixture was extracted with dichloromethane to obtain intermediate (V). This intermediate was used directly in the next reaction without further purification. Example 10

[0027] At 0℃, 250 mL of THF solution containing 26.0 g (0.1 mol) of intermediate (IV) was added to 105 mL of 2.1 M n-BuLi / n-hexane solution and stirred for 5 min. Then, 60 mL of HMAP and 35.4 g (0.22 mol) were added. N,N 50 mL of dimethylaminophosphoryl dichloride THF solution was stirred for 30 min, brought to room temperature, and reacted overnight. The THF was removed by vacuum distillation, water was added, and the mixture was extracted with dichloromethane to obtain intermediate (V). This intermediate was used directly in the next reaction without further purification. Example 11

[0028] At 0℃, 250 mL of THF solution containing 26.0 g (0.1 mol) of intermediate (IV) was added to 115 mL of 2.1 M n-BuLi / n-hexane solution and stirred for 5 min. Then, 50 mL of HMAP and 40.2 g (0.24 mol) were added. N,N 50 mL of dimethylaminophosphoryl dichloride THF solution was stirred for 30 min, brought to room temperature, and reacted overnight. The THF was removed by vacuum distillation, water was added, and the mixture was extracted with dichloromethane to obtain intermediate (V). This intermediate was used directly in the next reaction without further purification. Example 12

[0029] 34.9 g (0.1 mol) of intermediate (V) in 50 mL of n-hexane solution was added to 3.45 g Li / 31 mL NH3 (L) solution and reacted at room temperature for 15 min. Solid ammonium chloride was added, ammonia was distilled off, and the mixture was extracted with n-hexane. The intermediate (VI) was purified by silica gel column chromatography with a yield of 98.1%. Example 13

[0030] 34.9 g (0.1 mol) of intermediate (V) in 50 mL of n-hexane solution was added to 4.1 g Li / 33 mL NH3 (L) solution and reacted at room temperature for 15 min. Solid ammonium chloride was added, ammonia was distilled off, and the mixture was extracted with n-hexane. The intermediate (VI) was purified by silica gel column chromatography with a yield of 98.3%. Example 14

[0031] 24.0 g (0.1 mol) of intermediate (VI) was added to H2O / THF (volume ratio 1:8), stirred, and then 11.4 g (0.1 mol) of TFA was added. The mixture was reacted at room temperature for 1 h. THF was removed by vacuum distillation. The residue was added with an appropriate amount of water, extracted with n-hexane, dried, and concentrated to obtain intermediate (VII), which was used directly in the next reaction. Example 15

[0032] 19.6 g (0.1 mol) of intermediate (VII) was dissolved in 200 mL of ethanol, 2 g of 10% Pd-C was added, hydrogen gas was bubbled through at room temperature, and the reaction was carried out for 2 h. The mixture was filtered, the filtrate was evaporated to dryness under reduced pressure, and the residue was added to 10.6 g (0.1 mol) of acetic anhydride and 10.1 g (0.1 mol) of triethylamine. The mixture was reacted at 8 °C for 3 h, water was added, hexane was extracted, dried, concentrated, and purified to obtain (Z / E) 8-dodecene-1-ol acetate, with a yield of 94.7%. GC [column: HP-5MS (30 m × 0.32 mm × 0.25 μm), injection temperature 250 °C, detector temperature 300 °C, split ratio 30:1, flow rate 1 mL / min] determination: Z / E = 94:6; 1H NMR (300MHz, CDCl3) Z-isomer: δ 0.88 (t, J =7Hz, 3H), 1.30(m, 10H), 1.57(m, 2H), 1.97(m, 7H), 3.98(m, 2H), 5.26(m, 2H); E-isomer: δ 0.88 (t, J =7Hz, 3H), 1.32(m, 10H), 1.57(m, 2H), 1.98(m,7H), 3.97(m, 2H), 5.30(m, 2H). Example 16

[0033] 19.6 g (0.1 mol) of intermediate (VII) was dissolved in 200 mL of ethanol, 2.5 g of 10% Pd-C was added, hydrogen gas was introduced at room temperature, and the reaction was carried out for 2 h. The mixture was filtered, the filtrate was evaporated to dryness under reduced pressure, and 11.1 g (0.105 mol) of acetic anhydride and 8.3 g (0.105 mol) of pyridine were added to the residue. The mixture was reacted at 11 °C for 3 h, water was added, hexane was extracted, dried, concentrated, and purified to give (Z / E) 8-dodecene-1-ol acetate, with a yield of 96.3% and Z / E = 95:5. Example 17

[0034] 19.6 g (0.1 mol) of intermediate (VII) was dissolved in 200 mL of ethanol, 2 g of 10% Pd-C was added, hydrogen gas was introduced at room temperature, and the reaction was carried out for 2 h. The mixture was filtered, the filtrate was evaporated to dryness under reduced pressure, and 11.2 g (0.11 mol) of acetic anhydride and 8.7 g (0.11 mol) of pyridine were added to the residue. The mixture was reacted at 9 °C for 3 h, water was added, hexane was extracted, dried, concentrated, and purified to obtain (Z / E) 8-dodecene-1-ol acetate with a yield of 95.9% and Z / E = 95:5.

[0035] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing the pear fruit moth pheromone (Z / E)-8-dodecene-1-ol acetate, characterized in that, The preparation method includes the following steps: ， (1) 1,8-Octaic acid reacts with SOCl2 to give the corresponding acyl chloride (I); (2) 5% Pd-BaSO4 was suspended in dry THF, 2,6-dimethylpyridine was added, the mixture was stirred, hydrogen gas was passed through to a certain pressure, acyl chloride (I) was added, and the mixture was reacted at 25-30℃ to obtain intermediate (II). No purification treatment was required, and it was directly used in the next step of the reaction. (3) Add ethylene glycol to toluene. p -TsOH and intermediate (II) were refluxed to separate water, yielding intermediate (III); (4) Under N2 atmosphere, zinc powder was suspended in THF, intermediate (III) was added, cooled to -5℃, and a THF solution of n-butyraldehyde and TiCl4 was slowly added. The reaction was carried out at 0℃, and after post-treatment, intermediate (IV) was obtained. (5) Intermediate (IV) is dissolved in THF, and n-BuLi, HMPA and N, N -Dimethylaminophosphoryl dichloride, reacted at room temperature, to give intermediate (V), which can be used directly in the next reaction without purification; (6) Intermediate (V) is dissolved in n-hexane and reacted in Li / liquid NH3 to prepare intermediate (VI); (7) Intermediate (VI) is added to H2O / THF, then TFA is added, and the reaction is carried out at room temperature to obtain intermediate (VII). (8) Intermediate (VII) is dissolved in ethanol, 10% Pd-C is added, hydrogen is introduced at room temperature for reduction, filtered, the filtrate is evaporated under reduced pressure, and the residue is reacted with acetic anhydride / triethylamine or acetic anhydride / pyridine to obtain (Z / E)-8-dodecene-1-ol acetate.

2. The preparation method according to claim 1, characterized in that, The specific operation of step (1) is as follows: 1,8-octanedioic acid is mixed with 2 times the amount of SOCl2, heated under reflux for 1.5-2 hours, and excess SOCl2 is distilled off under reduced pressure to obtain acyl chloride (I).

3. The preparation method according to claim 1, characterized in that, The specific operation of step (2) is as follows: 5% Pd-BaSO4 of a certain mass fraction is suspended in dry THF, 2,6-dimethylpyridine is added, stirred, hydrogen gas is passed through to 1-2 atm, acyl chloride (I) is added, the reaction is carried out at 25-30℃ for 1-2 h, filtered, THF is distilled off under reduced pressure, n-hexane is added, filtered, concentrated, and intermediate (II) is obtained. It does not need to be purified and can be used directly in the next step of the reaction.

4. The preparation method according to claim 1, characterized in that, The specific operation of step (3) is as follows: add 6-10% by mass to toluene. p -TsOH, stir, then add ethylene glycol and intermediate (II), reflux to remove water for 5-6 hours, remove toluene by vacuum distillation, purify, and obtain intermediate (III).

5. The preparation method according to claim 1, characterized in that, The specific operation of step (4) is as follows: under N2 atmosphere, zinc powder is suspended in THF, intermediate (III) is added, stirred, cooled to -5℃, n-butyraldehyde and TiCl4 / THF solution are slowly added, stirred for 20 min, heated to 0℃, reacted for 2-2.5 h, 10% K2CO3 solution is added, stirred, THF is removed by vacuum distillation, extracted with dichloromethane, dried with anhydrous sodium sulfate, filtered, concentrated, purified, and intermediate (IV) is obtained.

6. The preparation method according to claim 1, characterized in that, The specific operation of step (5) is as follows: at 0°C, the THF solution of intermediate (IV) is added to the n-BuLi / n-hexane solution, stirred for 5 minutes, and then HMPA and N, N A THF solution of dimethylaminophosphoryl dichloride was stirred for 30 minutes, brought to room temperature, and reacted overnight. The THF was then distilled off under reduced pressure, water was added, and the mixture was extracted with dichloromethane to obtain intermediate (V). This intermediate was used directly in the next reaction without further purification.

7. The preparation method according to claim 1, characterized in that, The specific operation of step (6) is as follows: add the n-hexane solution of intermediate (V) to Li / liquid NH3 solution, react at room temperature for 15-30 min, add solid ammonium chloride, distill off ammonia, extract with n-hexane, separate and purify by silica gel column chromatography, and obtain intermediate (VI).

8. The preparation method according to claim 1, characterized in that, The specific operation of step (7) is as follows: add intermediate (VI) to H2O / THF with a volume ratio of 1:8, stir, add TFA, react at room temperature for 1 hour, remove THF under reduced pressure, extract the residue with n-hexane, dry, concentrate, and obtain intermediate (VII), which can be directly used for the next step of the reaction.

9. The preparation method according to claim 1, characterized in that, The specific operation of step (8) is as follows: intermediate (VII) is dissolved in ethanol, 10% Pd-C is added, hydrogen is introduced at room temperature, the reaction is carried out for 1 hour, filtered, the filtrate is evaporated under reduced pressure, the residue is added to acetic anhydride / triethylamine or acetic anhydride / pyridine, the reaction is carried out at 8-11℃ for 3 hours, water is added, hexane is extracted, dried, concentrated, purified, and (Z / E) 8-dodecene-1-ol acetate is obtained.

10. The preparation method according to claim 1, characterized in that, In step (2), the molar ratio of acyl chloride (I) to 2,6-dimethylpyridine is 1:2-2.2, and the mass fraction of 5% Pd-BaSO4 is 10%; in step (3), the molar ratio of intermediate (II) to ethylene glycol is 1:1; in step (4), the molar ratio of intermediate (III) to n-butyraldehyde, zinc powder, and TiCl4 is 1:1-1.2:3-3.3:1.3-1.5; in step (5), the molar ratio of intermediate (IV) to n-BuLi, N, N The molar ratio of dimethylaminophosphoryl dichloride is 1:2.2-2.5:2.2-2.5, and the volume ratio of THF to HMPA is 5-6:1; in step (6), the molar ratio of intermediate (V) to Li is 1:5-6, and the mass-volume ratio of Li / liquid NH3 is 1 g / 8-9 mL; in step (7), the molar ratio of intermediate (VI) to TFA is 1:1; in step (8), the molar ratio of intermediate (VII) to Ac2O and Et3N is 1:1-1.1:1-1.1.

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