阅读说明：本技术 一种制备(z,e)-12-十四碳烯-1-醇乙酸酯的改进方法 (Improved method for preparing (Z, E) -12-tetradecene-1-alcohol acetate ) 是由 江忠萍 李金涛 王滢秀 张作山 刘钦胜 左伯军 刘敬民 蒋爱忠 刘军 王霞 于 2020-12-29 设计创作，主要内容包括：本发明提供一种制备(Z,E)-12-十四碳烯-1-醇乙酸酯的改进方法,wittig反应中的溶剂体系,创新地引入三溶剂体系,增加试剂在反应体系的溶解度,降低溶剂整体凝固点,双重作用下避免反应过程中在较低温度下出现团聚现象,避免反应搅拌不畅和产生大量杂质,进而加大后处理难度；用冰乙酸终止反应,代替之前的含水稀酸,控制原料中剩余的醛类的缩合,避免大量杂质产生,缩合产物一旦产生对三苯氧膦和主产物烯醇溶解度较大,且分离不开,会极大加强后处理难度,产物提取损失大；同时由于反应能在0摄氏度左右以均相状态反应,转化彻底,收率大幅提高,后处理简单,副产物三苯氧膦以颗粒状析出,无大量泥状废弃物,无其它固废。(The invention provides an improved method for preparing (Z, E) -12-tetradecene-1-alcohol acetate, wherein a solvent system in a wittig reaction is innovatively introduced into a three-solvent system, the solubility of a reagent in the reaction system is increased, the integral solidifying point of the solvent is reduced, the agglomeration phenomenon at a lower temperature in the reaction process is avoided under the double actions, the unsmooth reaction stirring and the generation of a large amount of impurities are avoided, and the post-treatment difficulty is further increased; glacial acetic acid is used for stopping the reaction, the previous aqueous dilute acid is replaced, the condensation of the residual aldehydes in the raw materials is controlled, the generation of a large amount of impurities is avoided, once the condensation product generates triphenylphosphine oxide and the main product enol, the solubility is high, the separation is not easy, the post-treatment difficulty is greatly enhanced, and the extraction loss of the product is large; meanwhile, the reaction can be carried out in a homogeneous phase state at about 0 ℃, so that the conversion is thorough, the yield is greatly improved, the post-treatment is simple, the by-product triphenylphosphine oxide is separated out in a granular form, and a large amount of mud-shaped waste and other solid waste are avoided.)

1. An improved method for synthesizing (Z, E) -12-tetradecene-1-ol acetate compound, which is characterized by comprising the following steps:

(1) adding 1, 12-dibromododecane and triphenylphosphine into toluene, heating and refluxing for reaction, and separating and removing the toluene after the reaction is finished to obtain omega-bromododecyl triphenyl phosphonium bromide salt;

(2) dissolving omega-bromododecyl triphenyl phosphonium bromide salt in a mixed solvent, slowly adding organic base after cooling under the protection of nitrogen, stirring and reacting, continuously cooling to-10-0 ℃, adding acetaldehyde diluted by the solvent, carrying out heat preservation reaction at the temperature, adding glacial acetic acid after the reaction is finished, extracting a water phase by ethyl acetate, concentrating to obtain a solid, extracting the solid by petroleum ether, filtering to obtain triphenylphosphine oxide, and concentrating the solution to obtain liquid omega-bromotetradecene;

(3) adding omega-bromotetradecene into benzene, adding sodium hydroxide aqueous solution for hydrolysis, separating an organic layer after hydrolysis is finished, washing with water, drying, and distilling to obtain (Z, E) -12-tetradecene-1-alcohol;

(4) mixing (Z, E) -12-tetradecene-1-ol with pyridine and acetic anhydride, reacting at normal temperature, separating out a product after the reaction is finished, and performing silica gel column chromatography to obtain (Z, E) -12-tetradecene-1-ol acetate;

(5) and (3) heating the product in the step (4) under the protection of nitrogen, sequentially adding a sodium nitrite solution and a nitric acid solution, separating the product after the reaction is finished, and performing silica gel column chromatography to obtain the configuration-converted (Z, E) -12-tetradecene-1-alcohol acetate.

2. The process according to claim 1, wherein the molar ratio of 1, 12-dibromododecane to triphenylphosphine in step (1) is from 1.0:1.0 to 1.3, and the molar concentration of 1, 12-dibromododecane is from 0.5mol/L to 2.0 mol/L.

3. The method of claim 1, wherein the molar ratio of the ω -bromododecyltriphenylphosphonium bromide salt, the organic base, and the acetaldehyde in the step (2) is in the range of 1.0:1.1 to 2.0:1.0 to 1.3, and the molar concentration of the ω -bromododecyltriphenylphosphonium bromide salt is in the range of 0.3mol/L to 2.0 mol/L.

4. The method of claim 1, wherein the mixed solvent in step (2) is a mixture of tetrahydrofuran, diethylene glycol dimethyl ether and toluene, and the volume ratio is as follows: 1.0-10:1.0: 1.0-3.0.

5. The method of claim 1, wherein the organic base is dimethyl sulfoxide sodium salt, the molar concentration of the dimethyl sulfoxide sodium salt is 0.3mol/L-3.0mol/L, and the mass concentration of the glacial acetic acid is 99.5%.

6. The method of claim 1, wherein in step (3) the molar concentration of ω -bromotetradecene is 0.5mol/L to 1.5mol/L, the concentration of the aqueous sodium hydroxide solution is 2.0mol/L to 8mol/L, and the hydrolysis is carried out at 40 ℃ to 50 ℃ for 2h to 10 h.

7. The process according to claim 1, wherein the molar ratio of the (Z, E) -12-tetradecene-1-ol to the acetic anhydride in the step (4) is 1.0 to 1.2, and the molar concentration of the (Z, E) -12-tetradecene-1-ol is 1.0mol/L to 3.0 mol/L.

8. The method according to claim 1, wherein the molar ratio of the (Z, E) -12-tetradecene-1-ol acetate to the sodium nitrite solution and the nitric acid solution in the step (5) is in the range of 1.0:0.05 to 0.2:0.1 to 0.2.

Technical Field

The invention relates to a preparation method of Asiatic corn borer sex pheromone, in particular to an improved method for preparing (Z, E) -12-tetradecene-1-alcohol acetate, belonging to the technical field of biological pesticides.

Background

Asiatic corn borer (Ostrinia furnacalis) belongs to Lepidoptera, Orthosiphon family. The corn is mainly distributed in Asia, and other corn planting areas are distributed in China except the corn area of the Qinghai-Tibet plateau, and the main distribution areas are located in the three provinces of northeast, the North river, the south river, the east of Shandong, the Sichuan and the Guangxi province. The edible impurity mainly harms the corn, is the first big pest in corn production, has up to 25 host plants, and can also be harmful to sorghum, millet, cotton, hemp, wheat, barley, potato, beans, sunflower, sugarcane, sugar beet, tomato, eggplant and the like. Harming each part of the corn plant, leading the damaged part to lose the function and reducing the yield of the seeds. In the heart-leaf stage of corn, most of the newly hatched larvae climb into heart leaves to gather and eat heart-leaf mesophyll, and white film-shaped epidermis in a flower leaf shape is left; 2. most of the 3 rd larvae climb into heart leaves and are hidden as pests, and the heart leaves are unfolded to form regular row holes; then, the stems are continuously damaged by being eaten, and a large amount of excrement residues are often piled at the openings of the wormholes; the tassel is damaged and is easy to break, thus influencing pollination; the bracts and filaments are eaten by the moths, causing grain deficiency and blighted grains; the stalks, the ear stalks and the ear stalks are eaten to form tunnels, so that the transmission of water and nutrients in plants is damaged, the stalk folding rate is increased, and the seed yield is reduced; the newly hatched larvae can silken and droop, and spread to adjacent plants along with wind drift.

The corn is the first large grain variety in China, occupies 42 percent of the grain planting area, the seeding area of the Chinese corn in 2019 reaches 4128 ten thousand hectares, and the corn yield reaches 2.57 hundred million tons. Asiatic corn borers are world-wide large-scale insect pests with eating habits, the yield of spring corns is reduced by about 10 percent generally, the yield of summer corns is reduced by 20-30 percent, the yield of summer corns is reduced by over 50 percent in large-scale growing years, and the highest is the northern spring corn region and Huang-Huai plain spring and summer corn region.

Because chemical pesticides are used for preventing and treating the Asiatic corn borers for a long time in agricultural production, and the characteristics of boring property, long moth-developing period and the like of larvae of the Asiatic corn borers lead to poor using effect of the chemical pesticides, increase of resistance, reduction of prevention effect, reduction of the number of natural enemies and damage of agricultural ecological environment. The insect sex pheromone is a biological pesticide with strong specificity, no residue and environmental protection, and the biological technology for preventing and controlling insect pests of the insect sex pheromone becomes the agricultural green ecological prevention and control main pushing technology.

The Asiatic corn borer sex pheromone is a mixture of (Z, E) -12-tetradecene-1-alcohol acetate, the cis-trans ratio is close to 1:1, and the total synthesis yield is only 30% at home and abroad.

The currently reported synthetic method of the sex pheromone of the ostrinia nubilalis mainly comprises three reaction routes, namely an alkynol intermediate route, a hydroboration reaction route and a wittig reaction route. Wherein, the raw materials of the alkynol route are expensive, the reaction conditions are harsh, the synthesis route is long, and the industrialization is difficult; the hydrogenation reaction route has the advantages of difficult obtainment of raw materials, high price, rigorous reaction conditions and unsuitability for industrialization; the wittig reaction route is divided into two reaction routes, wherein the first reaction route takes 1, 12-dodecanediol as a raw material, aldehyde is obtained through selective acetylation and oxidation, and double bonds are obtained through wittig reaction with ethyl triphenyl phosphonium bromide. And secondly, 1, 12-dodecanediol is used as a raw material, is selectively brominated, salified with triphenylphosphine and subjected to wittig reaction with micromolecular aldehyde to obtain double bonds.

Therefore, the second method in the wittig reaction route is worth optimizing and has important significance for application and popularization of the sex pheromone of the ostrinia nubilalis.

Disclosure of Invention

The invention aims to provide a synthetic improvement method of Asiatic corn borer sex pheromone (Z, E) -12-tetradecene-1-alcohol acetate aiming at a second method in a wittig reaction route, so as to solve the problems of more impurities, difficult reaction control, easy agglomeration, difficult post-treatment and the like in the process. According to the method, a solvent system in the wittig reaction is preferably selected, a three-solvent system is innovatively introduced, the solubility of a wittig reagent in a reaction system is increased, the integral freezing point of the solvent is reduced, the agglomeration phenomenon at a lower temperature in the wittig reaction process is avoided under the double effects, the unsmooth reaction stirring and the generation of a large amount of impurities are avoided, and the post-treatment difficulty is further increased; glacial acetic acid is used for stopping the reaction in the wittig reaction post-treatment to replace the prior aqueous dilute acid, the condensation of the residual aldehydes in the raw materials is controlled, the generation of a large amount of impurities is avoided, the solubility of the condensation product generated once p-triphenyl phosphine oxide and the main product enol are high, the condensation product cannot be separated, the post-treatment difficulty is greatly enhanced, and the extraction loss of the product is large; meanwhile, the reaction can be carried out in a homogeneous phase state at about 0 ℃, so that the conversion is thorough, the yield is greatly improved, the post-treatment is simple, the by-product triphenylphosphine oxide is separated out in a granular form, and a large amount of mud-shaped waste and other solid waste are avoided.

The technical scheme adopted by the invention is as follows:

an improved method for synthesizing (Z, E) -12-tetradecene-1-ol acetate compound comprises the following steps:

(1) adding 1, 12-dibromododecane and triphenylphosphine into toluene, heating and refluxing for 8-50 h, separating and removing a toluene layer after the reaction is finished, and removing residual toluene to obtain omega-bromododecyl triphenyl phosphonium bromide;

(2) dissolving omega-bromododecyl triphenyl phosphonium bromide salt in a mixed solvent, slowly adding organic base after cooling to 20-30 ℃ under the protection of nitrogen, stirring and reacting for 1-1.5h, cooling to-10-0 ℃, adding acetaldehyde diluted by the solvent, keeping the temperature and reacting for 3-10h, adding glacial acetic acid after the reaction is finished, extracting a water phase by ethyl acetate, concentrating to obtain white to slightly yellowish solid, extracting the white to slightly yellowish solid by petroleum ether, filtering to obtain white granular triphenyl phosphine oxide, and concentrating the solution to obtain yellow liquid omega-bromotetradecene;

(3) adding omega-bromotetradecene into benzene, adding sodium hydroxide aqueous solution for hydrolysis, separating an organic layer after hydrolysis is finished, washing with water, drying, and distilling to obtain (Z, E) -12-tetradecene-1-alcohol;

(4) mixing (Z, E) -12-tetradecene-1-alcohol and pyridine with acetic anhydride, reacting at normal temperature for 8-24 h, separating out the product after the reaction is finished, and performing silica gel column chromatography to obtain (Z, E) -12-tetradecene-1-alcohol acetate. The Z/E molar ratio in the product was 95: 5.

(5) And (3) heating the product in the step (4) under the protection of nitrogen, sequentially adding a sodium nitrite solution and a nitric acid solution, separating the product after the reaction is finished, and performing silica gel column chromatography to obtain the configuration-converted (Z, E) -12-tetradecene-1-alcohol acetate. The Z/E molar ratio in the product was 24: 76.

The molar ratio of the 1, 12-dibromododecane to the triphenyl phosphine in the step (1) is 1.0:1.0-1.3, and the molar concentration of the 1, 12-dibromododecane is 0.5mol/L-2.0 mol/L.

The molar ratio of the omega-bromododecyl triphenyl phosphonium bromide salt, the organic base and the acetaldehyde in the step (2) is between 1.0:1.1 and 2.0:1.0 and 1.3, and the molar concentration of the omega-bromododecyl triphenyl phosphonium bromide salt is between 0.3mol/L and 2.0 mol/L. The mixed solvent in the step (2) is a mixed solution of tetrahydrofuran, diethylene glycol dimethyl ether and toluene, and the volume ratio is as follows: 1.0-10:1.0: 1.0-3.0. The organic alkali adopts dimethyl sulfoxide sodium salt, and the molar concentration of the dimethyl sulfoxide sodium salt is 0.3-3.0 mol/L. The mass concentration of the glacial acetic acid is 99.5%.

In the step (3), the molar concentration of the omega-bromotetradecene is 0.5mol/L-1.5mol/L, the concentration of the sodium hydroxide aqueous solution is 2.0 mol/L-8 mol/L, and the hydrolysis is carried out for 2h-10h at the temperature of 40 ℃ to 50 ℃.

The molar ratio of the (Z, E) -12-tetradecene-1-ol to the acetic anhydride in the step (4) is 1.0 to 1.2, and the molar concentration of the (Z, E) -12-tetradecene-1-ol is 1.0mol/L to 3.0 mol/L.

In the step (5), the molar ratio of the (Z, E) -12-tetradecene-1-ol acetate to the sodium nitrite solution to the nitric acid solution is 1.0:0.05-0.2: 0.1-0.2.

The synthesis improvement method takes 1, 12-dibromododecane as an initial raw material, and the initial raw material undergoes a salt forming reaction with triphenylphosphine, then undergoes a wittig reaction with acetaldehyde, then undergoes a hydrolysis reaction, an acetylation reaction and an isomer conversion reaction, and finally obtains a target product (Z, E) -12-tetradecene-1-ol acetate as a reference route, wherein by preferably selecting a solvent system in the wittig reaction, the solubility of a wittig reagent in a reaction system is increased, the integral freezing point of the solvent is reduced, the agglomeration phenomenon in the reaction process is avoided, the unsmooth reaction stirring and the generation of a large amount of impurities are avoided, and further the post-treatment difficulty is increased; glacial acetic acid is used for stopping the reaction in the wittig reaction post-treatment, the condensation of aldehydes is controlled, and a large amount of impurities are avoided; meanwhile, the reaction can be carried out in a homogeneous phase state at about 0 ℃, so that the conversion is thorough, the yield is greatly improved, the post-treatment is simple, the by-product triphenylphosphine oxide is separated out in a granular form, and a large amount of mud-shaped waste and other solid waste are avoided.

The invention has the beneficial effects that:

(1) by preferably selecting a solvent system in the wittig reaction, the solubility of a wittig reagent in the reaction system is increased, the integral solidifying point of the solvent is reduced, the agglomeration phenomenon in the reaction process is avoided, the unsmooth reaction stirring and the generation of a large amount of impurities are avoided, and the post-treatment difficulty is further increased;

(2) glacial acetic acid is used for stopping the reaction in the wittig reaction post-treatment, the condensation of aldehydes is controlled, and a large amount of impurities are avoided;

(3) as the reaction can be carried out in a homogeneous phase state at about 0 ℃, the conversion is thorough, the yield is greatly improved, the post-treatment is simple, the by-product triphenylphosphine oxide is separated out in a granular form, and a large amount of mud-like waste and other solid wastes are avoided.

Drawings

FIG. 1 shows a synthetic route of (Z, E) -12-tetradecene-1-ol acetate according to the present invention.

FIG. 2 shows the structural formula of (Z, E) -12-tetradecene-1-ol acetate.

FIG. 3 is a GC spectrum of (Z, E) -12-tetradecene-1-ol acetate with predominant Z-form.

FIG. 4 is a spectral data analysis of FIG. 3.

FIG. 5 shows the GC spectrum of (Z, E) -12-tetradecene-1-ol acetate with predominant form E.

FIG. 6 is a spectral data analysis of FIG. 5.

FIG. 7 is a GC-MS spectrum of (Z, E) -12-tetradecene-1-ol acetate.

Detailed Description

The following examples are further illustrated.

Example 1

(1) Omega-bromododecyl triphenyl phosphonium bromide salt synthesis

32.80(100mmol) of 1, 12-dibromododecane and 26.20(100mmol) of triphenylphosphine are put into 300ml of toluene and heated under reflux for 18 hours, a toluene layer is formed when the reaction is finished, and residual toluene is removed to obtain 51.39g of omega-bromododecyl triphenyl phosphonium bromide, wherein the yield is 87.1%.

(2) Omega-bromotetradecene synthesis

47.20g (80mmol) of omega-bromo quaternary phosphonium salt is added into a mixed solvent (50ml tetrahydrofuran, 10ml diethylene glycol dimethyl ether and 20ml toluene) under the protection of nitrogen, stirring to dissolve, maintaining the temperature at 20 ℃, slowly adding 50ml of 2.5mol/L tetrahydrofuran solution of dimethyl sulfoxide sodium salt, stirring to react for 1h, then cooling to-10 ℃, adding 3.9g (84mmol) of acetaldehyde, carrying out heat preservation reaction for 6h, carrying out TLC tracking detection, adding glacial acetic acid after the raw materials are reacted, extracting a water phase by ethyl acetate, concentrating to obtain a white to yellowish solid, extracting the white to yellowish solid by 200ml of petroleum ether, filtering to obtain white granular triphenyl phosphine oxide, concentrating a filtrate to obtain a yellow liquid omega-bromotetradecene crude product, and carrying out silica gel column chromatography to obtain the 15.70g Z type omega-bromotetradecene with the main yield of 71.3%.

(3) Synthesis of (Z, E) -12-tetradecene-1-ol

27.5g (100mmol) of omega-bromotetradecene is added into 200ml of benzene, 2.5M sodium hydroxide aqueous solution 60ml is added, hydrolysis is carried out for 8h at the temperature of 40-50 ℃, an organic layer is separated after the hydrolysis is finished, and the organic layer is washed by water, dried by anhydrous sodium sulfate, distilled and chromatographed by silica gel column, thus obtaining 19.75g Z type-dominant (Z, E) -12-tetradecene-1-ol with the yield of 93.1 percent.

(4) Synthesis of (Z, E) -12-tetradecene-1-ol acetate

42.40g (200mmol) of (Z, E) -12-tetradecene-1-ol, 100mL of pyridine and 21.0g (200mmol) of acetic anhydride are reacted at normal temperature for 20h, after the reaction is finished, a product is separated, and silica gel column chromatography is carried out to obtain (Z, E) -12-tetradecene-1-ol acetate with 48.81g Z type as the main component, wherein the yield is 96.1 percent, and the Z/E ratio is 95: 5.

(5) Configurational transformation of (Z, E) -12-tetradecene-1-ol acetate

And (3) putting 20.2g of the product in the step (4) into a flask, heating to 80 ℃ under the protection of nitrogen, dropwise adding 5.0ml (2mol/L) of sodium nitrite solution, dropwise adding 3.4ml (2mol/L) of nitric acid solution, and continuing to react for 5 hours. After cooling to room temperature, 10ml of n-hexane was added, and the mixture was washed with a saturated sodium carbonate aqueous solution, water and a saturated saline solution and dried over anhydrous sodium sulfate. Filtering, concentrating, and performing column chromatography to obtain colorless liquid 20.1g, with yield about 100%, and Z/E ratio 24: 76.

Example 2

(1) Omega-bromododecyl triphenyl phosphonium bromide salt synthesis

32.80(100mmol) of 1, 12-dibromododecane and 28.82(110mmol) of triphenylphosphine are put into 300ml of toluene and heated under reflux for 18 hours, a toluene layer is formed when the reaction is finished, and residual toluene is removed to obtain 51.86g of omega-bromododecyl triphenyl phosphonium bromide, wherein the yield is 87.9%.

(2) Omega-bromotetradecene synthesis

Under the protection of nitrogen, 59.00g (50mmol) of omega-brominated quaternary phosphonium salt is added into a mixed solution of 50ml tetrahydrofuran, 10ml diethylene glycol dimethyl ether and 30ml toluene, the mixed solution is stirred and dissolved, the temperature is maintained at 20 ℃ to 30 ℃, 50ml tetrahydrofuran solution of 2.5mol/L dimethyl sulfoxide sodium salt is slowly added, the mixed solution is stirred and reacted for 1h, then the temperature is reduced to minus 10 ℃, 4.84g (110mmol) acetaldehyde is added, the heat preservation reaction is carried out for 6h, TLC tracking detection is carried out, glacial acetic acid is added after the raw material reaction is finished, the water phase is extracted by ethyl acetate and then concentrated to obtain white to slightly yellowish solid, the white to slightly yellowish solid is extracted by 200ml petroleum ether and then filtered to obtain white granular triphenoxy phosphine, the solution is concentrated to obtain yellow liquid omega-brominated tetradecene crude product, silica gel column chromatography is carried out to obtain 15.77g Z type omega-brominated tetradecene, the yield thereof was found to be 71.6%.

(3) Synthesis of (Z, E) -12-tetradecene-1-ol

27.50g (100mmol) of omega-bromotetradecene is added into 300ml of benzene, 5.0M of sodium hydroxide aqueous solution is added for 24ml, hydrolysis is carried out at 40-50 ℃ for 10h, an organic layer is separated after the hydrolysis is finished, and the organic layer is washed by water, dried by anhydrous sodium sulfate, distilled and chromatographed by silica gel column to obtain (Z, E) -12-tetradecene-1-ol with the main form of 19.92g Z, and the yield is 94.0%.

(4) Synthesis of (Z, E) -12-tetradecene-1-ol acetate

63.60g (300mmol) of (Z, E) -12-tetradecene-1-ol, 140mL of pyridine and 36.80g of acetic anhydride (360mmol) are reacted at normal temperature for 20h, after the reaction is finished, a product is separated, and silica gel column chromatography is carried out to obtain (Z, E) -12-tetradecene-1-ol acetate with 73.93gZ type as the main component, wherein the yield is 97.0 percent, and the Z/E ratio is 94.5: 5.5.

(5) Configurational transformation of (Z, E) -12-tetradecene-1-ol acetate

And (3) putting 20.2g of the product in the step (4) into a flask, heating to 75 ℃ under the protection of nitrogen, dropwise adding 5.0ml (2mol/L) of sodium nitrite solution, dropwise adding 3.4ml (2mol/L) of nitric acid solution, and continuing to react for 4 hours. After cooling to room temperature, 10ml of n-hexane was added, and the mixture was washed with a saturated sodium carbonate aqueous solution, water and a saturated saline solution and dried over anhydrous sodium sulfate. Filtering, concentrating, and performing column chromatography to obtain colorless liquid 20.1g, with yield about 100%, and Z/E ratio 25: 75.

Example 3

(1) Omega-bromododecyl triphenyl phosphonium bromide salt synthesis

65.60g (200mmol) of 1, 12-dibromododecane and 57.60(220mmol) of triphenylphosphine are put into 600ml of toluene and heated under reflux for 24 hours, a toluene layer is formed when the reaction is finished, and residual toluene is removed to obtain 107.387g of omega-bromododecyl triphenyl phosphonium bromide, wherein the yield is 91.0%.

(2) Omega-bromotetradecene synthesis

Under the protection of nitrogen, 70.80g (120mmol) of omega-brominated quaternary phosphonium salt is added into a mixed solution of 60ml of tetrahydrofuran and 12ml of diethylene glycol dimethyl ether 24ml of toluene, the mixture is stirred and dissolved, the temperature is maintained at 20 ℃ to 30 ℃, 60ml of tetrahydrofuran solution of 3.0mol/L dimethyl sulfoxide sodium salt is slowly added, the mixture is stirred and reacted for 1.5h, then the temperature is reduced to-5 ℃, the mixed solution of 6.34g (144mmol) of acetaldehyde and 16ml of tetrahydrofuran is dropwise added, the temperature is kept and the reaction is carried out for 10h, TLC tracking detection is carried out, glacial acetic acid is added after the raw material reaction is finished, a water phase is extracted by ethyl acetate and then concentrated to obtain white to slightly yellowish solid, the white to slightly yellowish solid is extracted by 300ml of petroleum ether and then filtered to obtain white granular triphenylphosphine oxide, a yellow liquid omega-bromotetradecene crude product is obtained after the solution is concentrated, silica gel column chromatography is carried out to obtain 15.770g Z type main omega, the yield thereof was found to be 71.6%.

Adjusting pH value to neutrality with 10% hydrochloric acid, extracting with diethyl ether, mixing organic phases, washing with saturated sodium chloride aqueous solution, drying with anhydrous sodium sulfate, distilling to obtain crude product, and performing silica gel column chromatography to obtain 23.46g omega-bromotetradecene with Z type as main component with yield of 71.1%.

(3) Synthesis of (Z, E) -12-tetradecene-1-ol

33.00g (60mmol) of omega-bromotetradecene is added into 300ml of benzene, 44ml of 3.0M sodium hydroxide aqueous solution is added, hydrolysis is carried out for 8h at the temperature of 40-50 ℃, an organic layer is separated after the hydrolysis is finished, and the organic layer is washed by water, dried by anhydrous sodium sulfate, distilled and chromatographed by silica gel to obtain (Z, E) -12-tetradecene-1-ol with the main form of 24.48g Z, wherein the yield is 96.2%.

(4) Synthesis of (Z, E) -12-tetradecene-1-ol acetate

30.88g (120mmol) of (Z, E) -12-tetradecene-1-ol, 120mL of pyridine and 24.40g of acetic anhydride (260mmol) are reacted at normal temperature for 18h, after the reaction is finished, a product is separated, and silica gel column chromatography is carried out to obtain (Z, E) -12-tetradecene-1-ol acetate mainly of 58.70gZ type, wherein the yield is 96.3 percent, and the Z/E ratio is 94.9: 5.1.

(5) Configurational transformation of (Z, E) -12-tetradecene-1-ol acetate

And (3) putting 20.2g of the product in the step (4) into a flask, heating to 75 ℃ under the protection of nitrogen, dropwise adding 5.0ml (2mol/L) of sodium nitrite solution, dropwise adding 3.4ml (2mol/L) of nitric acid solution, and continuing to react for 4 hours. After cooling to room temperature, 20ml of n-hexane was added, and the mixture was washed with a saturated sodium carbonate aqueous solution, water and a saturated saline solution and dried over anhydrous sodium sulfate. Filtering, concentrating, and performing column chromatography to obtain colorless liquid 20.1g, with yield about 100%, and Z/E ratio of 26: 74.

And (3) product analysis:

results of analysis of the products Z-12-tetradecene-1-ol acetate and E-12-tetradecene-1-ol acetate obtained in examples 1 to 3:

(1) gas Chromatography (GC) analysis

The analysis was carried out by Shimadzu GC-2010plus gas chromatograph. Column RTX-1701(30m ﹡ 0.25.25 mm ﹡ 0.25.25 μm); sample inlet temperature: 250 ℃; FID detector temperature: 250 ℃; the split ratio is as follows: 30: 1; column flow rate: 1 ml/min; temperature programming: keeping at 80 deg.C for 1min, and raising to 250 deg.C at a rate of 15 deg.C/min for 20 min.

The results of the analyses are shown in FIGS. 3 and 4, and show that the molar cis-trans ratio of Z-12-tetradecene-1-ol acetate to E-12-tetradecene-1-ol acetate is 94: 6. As shown in FIGS. 5 and 6, the results indicated that the molar cis-trans ratio of Z-12-tetradecene-1-ol acetate to E-12-tetradecene-1-ol acetate was 24: 76.

(2) Gas-mass spectrometry (GC-MS) analysis

And (3) analyzing by using a QP5050 gas-mass spectrometer. A chromatographic column: RTX-5(30m ﹡ 0.25mm ﹡ 0.25 μm); sample inlet temperature: 250 ℃, ion source temperature: 250 ℃; temperature programming: 80 ℃ for 1min, and up to 250 ℃ at a rate of 5 ℃/min for 20min, column flow: 1 ml/min.

The mass spectrum results are shown in FIG. 7, and the product was analytically determined to be (Z, E) -12-tetradecene-1-ol acetate.