阅读说明：本技术 一种2-十一烷氧基-1-乙醇的合成方法与应用 (Synthesis method and application of 2-undecyloxy-1-ethanol ) 是由 吕卫鹏 崔艮中 徐文泉 陈海勋 吴朋 于 2021-08-11 设计创作，主要内容包括：本发明公开了一种2-十一烷氧基-1-乙醇的合成方法,属于化工生产技术领域。本发明以1-溴代十一烷与乙二醇为初始原料,加入常用强碱,升温后采用一锅法进行反应最终合成所述2-十一烷氧基-1-乙醇。本发明公开的合成方法中反应条件温和可控,其是以廉价原材料为主,产品成本低,反应收率高,且产品含量可达到99％以上(GC检测),可适于工业化规模生产。此外利用本方法合成的2-十一烷氧基-1-乙醇可作为松褐天牛性信息素组分,并将其配制成诱芯结合诱捕器能有效诱杀松褐天牛雄虫。因此,本发明公开的技术方案极具市场应用与推广前景。(The invention discloses a synthetic method of 2-undecyloxy-1-ethanol, belonging to the technical field of chemical production. The 2-undecyloxy-1-ethanol is synthesized by taking 1-bromoundecane and ethylene glycol as initial raw materials, adding common strong base, heating and reacting by adopting a one-pot method. The synthesis method disclosed by the invention has mild and controllable reaction conditions, mainly uses cheap raw materials, has low product cost and high reaction yield, has the product content of over 99 percent (GC detection), and can be suitable for industrial mass production. In addition, the 2-undecyloxy-1-ethanol synthesized by the method can be used as a sex pheromone component of the monochamus alternatus hope, and the sex pheromone component can be prepared into a lure combined trap, so that the drone of the monochamus alternatus hope can be effectively trapped and killed. Therefore, the technical scheme disclosed by the invention has great market application and popularization prospects.)

1. The method for synthesizing 2-undecyloxy-1-ethanol is characterized by comprising the following steps:

1) mixing ethylene glycol, strong base and a homogeneous catalyst, heating for reaction, and then dropwise adding 1-bromoundecane for reaction to obtain a reaction solution;

2) separating the reaction solution, extracting, washing and concentrating to obtain a crude product;

3) and refining and purifying the crude product to obtain the 2-undecyloxy-1-ethanol.

2. The method for synthesizing 2-undecyloxy-1-ethanol according to claim 1, wherein the mass ratio of the ethylene glycol, the strong base and the 1-bromoundecane added in the step 1) is 8:1.0: 0.05.

3. The method for synthesizing 2-undecyloxy-1-ethanol according to claim 2, wherein the strong base is one of sodium hydroxide, lithium hydroxide, potassium hydroxide and rubidium hydroxide.

4. The method as claimed in claim 1, wherein the catalyst is one of palladium-anchored homogeneous catalyst, ruthenium-anchored homogeneous catalyst, and 18 crown 6 ether homogeneous catalyst.

5. The method for synthesizing 2-undecyloxy-1-ethanol according to any one of claims 1 to 4, wherein the temperature of the mixture of ethylene glycol, strong base and homogeneous catalyst is 50 ℃ to 150 ℃ and the reaction time is 1 to 10 hours.

6. The synthesis method of 2-undecyl alkoxy-1-ethanol according to any one of claims 1 to 4, characterized in that the temperature for dripping 1-bromoundecane is 25 ℃ to 50 ℃, and the dripping time is 0.5 to 5 hours; and dropwise adding 1-bromoundecane for reaction at the temperature of 50-150 ℃ for 2-10 h.

7. The method for synthesizing 2-undecyloxy-1-ethanol according to claim 1, wherein the extraction solvent in step 2) is one of toluene, petroleum ether, dichloromethane and diethyl ether.

8. The method for synthesizing 2-undecyloxy-1-ethanol according to claim 1, wherein in the step 3), the method for refining and purifying the crude product is chromatographic column separation or high vacuum rectification.

9. Use of 2-undecyloxy-1-ethanol synthesized according to the method of claim 1 in the sex pheromone fraction of monochamus alternatus hope.

Technical Field

The invention belongs to the technical field of chemical production and green pesticide synthesis, and relates to a novel synthetic method of sex pheromone components of monochamus alternatus hope. In particular to a synthesis method of 2-undecyloxy-1-ethanol and application thereof in sex pheromone components of monochamus alternatus.

Background

The monochamus alternatus hope is an important trunk-boring pest of Chinese pine and also a main vector insect of pine for destroying and damaging pine wood nematode disease. As an important forestry quarantine pest, the larva of the pest damages the phloem and xylem of the transportation and conduction tissue of the weakened pine trees, destroys the transportation of water and nutrient substances and causes withering of wood. During feeding and nutrition supplementing processes, adults bite the twigs and carry the pine wood nematodes to invade the pine trees, so that the pine trees are infected by wounds to cause weak growth, and finally die in a large area.

The larvae are mainly harmful to the insect state and are harmful to forest stands and are visible all the year round. The larvae which are hatched at first eat from phloem of inner cortex of trunk, and the larvae of 2 years old eat from sapwood and bite into curved, shallow and flat irregular wormholes; when the larvae grow to 3, 4 years old, the drilling of oblate invasion holes into xylem is started. The larva produces a clicking sound when eating and discharges a large amount of coarse fibrous bristled bits. If the population density in the trunk is quite high, the conducting tissues are damaged, so that nutrient delivery of the pine trees is interrupted, and the pine trees die. The time of eating is 3-11 months, and in the last 12 months, 4-year larvae overwinter in the trunk, and a few 3-year larvae overwinter.

The monochamus alternatus hope plays a key role in carrying, spreading and assisting pathogen invasion into host during the process of spreading and infection of the pine wood nematode. Natural enemies include pathogenic microorganisms, parasitic nematodes, parasitic insects, predatory insects, spiders, birds, and the like. The life history includes 4 stages of imago, egg, larva and pupa, and generation 1 occurs in one year, so that the mature larva overwinter in the tunnel. Distributed in china, korea, japan, and laos. Listed in the list of dangerous pests in forestry of the national forestry agency of China in 2003; it can cause destructive damage to pine trees, so it is of great significance to explore a synthetic method which is cheap and suitable for industrial scale production.

2-undecyloxy-1-ethanol is a component of monochamus alternatus pheromone and has physiological activity of attracting males. Although the biological activity of the pesticide is obvious, the content of the pesticide in the female polypide of the forestry pests is extremely low, and the pesticide is difficult to extract, so that the application research of the pesticide in the field of biological control of plant diseases and pests is hindered. Therefore, the research on the cheap method for synthesizing the 2-undecyloxy-1-ethanol is of great significance.

In addition, although the research on the synthesis of 2-undecyloxy-1-ethanol has been advanced, there still remain many problems such as low reaction yield, expensive raw materials, long reaction steps, inability of mass production, and the like. Therefore, the synthesis method has high research yield, mild reaction conditions and short reaction steps, and can be produced in a large scale, thereby having great application value for preventing and treating monochamus alternatus hope.

Disclosure of Invention

In view of the above, the present invention aims to provide a method for synthesizing 2-undecyloxy-1-ethanol, which is a novel sex pheromone component of monochamus alternatus.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a method for synthesizing 2-undecyloxy-1-ethanol specifically comprises the following steps:

1) mixing ethylene glycol, strong base and a homogeneous catalyst, heating for reaction, and then dropwise adding 1-bromoundecane for reaction to obtain a reaction solution;

2) separating the reaction solution, extracting, washing and concentrating to obtain a crude product;

3) and refining and purifying the crude product to obtain the 2-undecyloxy-1-ethanol.

Specifically, the route of the synthetic method of the 2-undecyloxy-1-ethanol is as follows:

preferably, in the step 1), the mass ratio of the ethylene glycol, the strong base and the 1-bromoundecane is 8:1.0: 0.05.

More preferably, the strong base is one of sodium hydroxide, lithium hydroxide, potassium hydroxide and rubidium hydroxide.

Preferably, the catalyst is one of a palladium anchored homogeneous catalyst, a ruthenium anchored homogeneous catalyst, and an 18 crown 6 ether homogeneous catalyst.

Further, the temperature of the mixture of the ethylene glycol, the strong base and the homogeneous catalyst is increased to 50-150 ℃, and the reaction time is 1-10 h.

Further, the temperature of dripping the 1-bromoundecane is 25-50 ℃, and the dripping time is 0.5-5 h; and dropwise adding 1-bromoundecane for reaction at the temperature of 50-150 ℃ for 2-10 h.

Preferably, the extraction solvent in step 2) is one of toluene, petroleum ether, dichloromethane and diethyl ether.

Preferably, in the step 3), the method for refining and purifying the crude product is chromatographic column separation or high vacuum rectification.

In addition, the invention also claims the application of the 2-undecyloxy-1-ethanol synthesized by the method in sex pheromone components of monochamus alternatus hope.

According to the technical scheme, compared with the prior art, the synthesis method and the application of the 2-undecyloxy-1-ethanol have the following excellent effects:

the 2-undecyloxy-1-ethanol is synthesized by taking 1-bromoundecane and ethylene glycol as initial raw materials, adding common strong base, heating and reacting by adopting a one-pot method. The synthesis method disclosed by the invention has mild and controllable reaction conditions, mainly uses cheap raw materials (the main raw materials are 7 yuan/kg of industrial grade ethylene glycol, 10 yuan/kg of industrial potassium hydroxide and about 1500 yuan/kg of production cost), has low product cost and high reaction yield, has the product content of over 99 percent (GC detection), and can be suitable for industrial scale production.

Furthermore, after the cheap, high-activity and high-selection homogeneous catalyst is used, the common strong base sodium hydride or metal sodium which is easy to explode and has a high danger coefficient in the original process is replaced by the common strong base, and the method has the advantages that the common strong base is very cheap, most of all, the common strong base is not dangerous and is not easy to combust and explode;

in addition, the 2-undecyloxy-1-ethanol synthesized by the method can be used as a sex pheromone component of the monochamus alternatus hope, and the sex pheromone component can be prepared into a lure combined trap which can effectively trap and kill the androphore of the monochamus alternatus hope. Therefore, the technical scheme disclosed by the invention has great market application and popularization prospects.

Detailed Description

The technical solutions disclosed in the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The embodiment of the invention discloses a synthetic method of 2-undecyloxy-1-ethanol, which has the advantages of high yield, mild reaction conditions and short reaction steps and can be used for large-scale production.

The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.

The technical solution of the present invention will be further described with reference to the following specific examples.

Example 1:

a synthetic method of 2-undecyloxy-1-ethanol specifically comprises the following steps:

adding 136.4g of ethylene glycol into a 250ml three-necked bottle, adding 12.6g of potassium hydroxide, adding a homogeneous catalyst 18 crown-6, heating to 85 ℃, and reacting for 3 hours; then, 42.8g of 1-bromoundecane is added dropwise, and the temperature is raised to 110 ℃ for reaction for 8 hours; extracting after separating liquid, merging organic phases, concentrating, and rectifying under high vacuum to obtain 32.4g of a product with the purity of 99%.

Example 2: pilot scale preparation

A synthetic method of 2-undecyloxy-1-ethanol specifically comprises the following steps:

(1) adding 1#16.38kg of ethylene glycol, 1.5kg of potassium hydroxide No. 2 and 290g of homogeneous catalyst No. 18 crown-63 into a 30L reaction kettle in sequence, heating and stirring to 85 ℃ for reaction for 32 hours;

(2) dripping No. 4 into the reaction kettle, heating to 110 ℃ after dripping, carrying out reflux stirring reaction, and sampling and reacting for 5 hours every 2 hours; detecting the reaction progress;

(3) stopping the reaction when the reaction raw material is below 10 percent and the reaction byproduct diether is below 9 percent;

(4) adding 5L of water into the reaction solution, stirring and inactivating, and separating liquid; wherein the water phase is extracted by 5L of 3PE, all organic phases are combined, 3.0kg of anhydrous sodium sulfate is added for drying, and the mixture is decompressed and concentrated to be dry, finally 5.1kg of crude product with 74.89 percent of content and 80.37 percent of yield is obtained, and the content can reach 99 percent after rectification and purification.

The inventive content is not limited to the content of the above-mentioned embodiments, wherein combinations of one or several of the embodiments may also achieve the object of the invention.

To further verify the excellent effects of the present invention, the inventors also conducted the following experiments:

installing traps in the forest of Shaanxi Ankang cow hoof mountain at 23-8-23 of 23.2020, wherein the interval of each trap is more than 120m, the distance from the bottom of a trap insect collecting bottle to the ground is not less than 1.5m, and 3 setting tests are hung per hectare, wherein the tests comprise 6 groups in total, A, B, C, D, E, F are different processes to obtain monochamus alternatus attractant with different purities, and C is the monochamus alternatus attractant related to the process; s1 and S2 are commercial monochamus alternatus attractants from two different manufacturers. When the device is installed, each group is divided into 8 groups, namely A1 group, B1 group, C1 group, D1 group, E1 group, F1 group, S1-1 group and S2-1 group. The number of Monochamus alternatus lures in each trap was collected and recorded every 15 days, and the lures were interchanged between groups.

The different treatments were differentially analyzed using the Dunca's test at a P <0.05 level using SPSS software. As can be seen from Table 1, the effect of trapping longicorn is obviously different for different attractants, wherein the effect of the pheromone attractant obtained by the invention is the best in the treatment C, the total trapping amount reaches 227 heads in the experiment period, and the trapping amounts are 171 and 146 heads in the treatment D and the treatment B respectively. Overall, treatment C achieved by the present invention was the best.

TABLE 1 different treatments for Ankang Tailing longicorn trapping

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.