CN110294664B - Synthetic method of 2-tetradecyne-1-ol - Google Patents
Synthetic method of 2-tetradecyne-1-ol Download PDFInfo
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- CN110294664B CN110294664B CN201910710665.4A CN201910710665A CN110294664B CN 110294664 B CN110294664 B CN 110294664B CN 201910710665 A CN201910710665 A CN 201910710665A CN 110294664 B CN110294664 B CN 110294664B
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- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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Abstract
The invention discloses a synthetic method of 2-tetradecyne-1-ol, belonging to the technical field of chemical production. The method takes acetylene as a starting material and reacts with alkali in a solvent to generate acetylene salt; then adding 1-bromoundecane for reaction to obtain 1-tridecyne salt, and further reacting with paraformaldehyde, formaldehyde water solution or formaldehyde gas to obtain 2-tetradecyne-1-alcohol by a one-pot synthesis method. The method has the advantages of mild reaction conditions, simple and convenient operation, low production cost, good economic benefit, popularization and application, and high purity and yield of the product 2-tetradecyne-1-ol.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a synthetic method of 2-tetradecyne-1-ol.
Background
Hyphantria cunea (Drury) of the American white moth belongs to Lepidotera of Lepidoptera and Arctidae of Arctidae, and is an important international quarantine pest. Because it has the characteristics of food impurity, large food intake, strong reproductive capacity, wide adaptability, high propagation speed, serious harm and the like, it becomes a significant foreign invasive pest in China and is the most dangerous invasive species at home and abroad at present.
The fall webworms are native to north China and distributed in the north latitude of 19-55 degrees, and then are introduced into Europe and Asia. Since the first discovery of the fall webworms in Dandong City of Liaoning province in 1979, the epidemic areas of China have spread to 586 county-level administrative districts of 13 provinces (city, autonomous region), and huge damage is caused to forest resources and ecological environment.
The fall of the hyphantria cunea host is wide, and researches in recent years show that the fall of the hyphantria cunea host is continuously expanded, and 630 various hosts are harmed worldwide, wherein more than 300 hosts are harmed in China. The favorite tree species include poplar, mulberry, phoenix tree, maple, etc., and also harm the broad-leaved tree species such as willow, locust tree, camptotheca acuminata, ailanthus altissima, etc. Besides trees and trees, the fertilizer also harms crops and vegetables. The larva of the fall webworm has large food intake, and can eat the leaves of the whole plant overnight during a major outbreak, so that the plant grows and develops badly, and even the tree dies and the crops and vegetables are not harvested in severe cases, so that serious harm is caused.
The invasion and propagation ways of the fall webworms are quite various, the enhancement of the monitoring of the insect situation is the basic work for preventing and controlling the fall webworms, and the method has important significance for timely taking prevention measures and preventing the spread of the epidemic situation. The method for trapping and monitoring male adults by using the hyphantria cunea sex trapper is a mature monitoring technology, and is high in monitoring result accuracy and remarkable in effect.
The major attracting active components of the sex pheromone of the fall webworm are (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene and (3Z, 6Z,9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosatriene, and the attracting active components are all obtained by deriving and synthesizing an intermediate 2-tetradecyne-1-ol through eight steps of reaction:
the hyphantria cunea pheromone has a complex chemical structure, multiple synthesis steps and high difficulty, so that the final yield is low; in order to produce an pheromone product meeting market demands, a production process of a basic compound 2-tetradecyne-1-ol must be solved, wherein the 2-tetradecyne-1-ol (Cas: 51309-22-9) is a white solid at room temperature, and the melting point is 42-44 ℃.
For 2-tetradecyne-1-ol, the currently reported synthesis methods include one of the following:
in a solvent system of hexamethylphosphoric triamide (HMPA) and Tetrahydrofuran (THF), propiolic alcohol and 1-bromoundecane are used as raw materials, n-butyl lithium is used as a base, and 2-tetradecyne-1-ol is synthesized [ J.Org.chem.2010, 75, 4619-4622].
The reaction needs to be carried out under strict anhydrous and anaerobic conditions and at the temperature of minus 78 ℃, the reaction conditions are harsh, the operation complexity is high, certain potential safety hazards exist, and the large-scale production is difficult to realize; therefore, the development of a high-efficiency and safe method for synthesizing 2-tetradecyne-1-ol and the realization of industrial production thereof have important practical significance.
Disclosure of Invention
The technical problem to be solved is as follows: how to obtain the synthesis method of the 2-tetradecyne-1-ol with mild reaction condition and simple reaction steps and obtain higher product yield and purity.
The technical scheme is as follows: in order to solve the problems, the technical scheme adopted by the invention is as follows:
a synthetic method of 2-tetradecyne-1-alcohol takes acetylene as a starting material and reacts with alkali to generate acetylene salt; then adding 1-bromoundecane to obtain 1-tridecyne salt, further reacting with paraformaldehyde, formaldehyde water solution or formaldehyde gas, and synthesizing by a one-pot method to obtain 2-tetradecyne-1-ol; the base is any one or a mixture of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium tert-butoxide, sodium hydrogen, N-butyl lithium, cesium hydroxide, calcium hydroxide, isopropylmagnesium bromide, methylmagnesium bromide or phenylmagnesium bromide, and the solvent is one or a mixture of water, methanol, ethanol, isopropanol, butanol, tetrahydrofuran, methyltetrahydrofuran, isopropyl ether, ethylene glycol dimethyl ether, DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), sulfolane, dichloromethane, chloroform, methyl tert-butyl ether, toluene or 1, 4-dioxane. The method comprises the following steps:
(1) Adding alkali and a solvent into a reaction vessel, stirring for dissolving, introducing acetylene gas under the condition of controlling the temperature to be-20-80 ℃ until a system is saturated, and reacting to generate acetylene salt; then dropwise adding the 1-bromoundecane solution, controlling the temperature and stirring to react for 2-5h after the dropwise adding is finished, and generating 1-tridecyne salt; the 1-bromoundecane solution is a 1-bromoundecane solution dissolved in the solvent, and the dosage ratio of the 1-bromoundecane to the solvent is 1-3mol:1L; the dosage ratio of the alkali to the solvent is 1-2mol:1L;
(2) Adding polyformaldehyde, formaldehyde water solution or formaldehyde gas into the reaction solution obtained in the step (1), controlling the temperature to be 0-100 ℃, reacting for 0.5-2h, and treating the reaction solution after the reaction is finished to obtain 2-tetradecyne-1-ol. The synthetic route is as follows:
in the synthesis method of the 2-tetradecyne-1-ol, the alkali is any one of sodium hydroxide, potassium tert-butoxide, sodium hydrogen, isopropyl magnesium bromide or methyl magnesium bromide.
According to the synthesis method of the 2-tetradecyne-1-ol, the solvent is one or a mixture of tetrahydrofuran, methyltetrahydrofuran, isopropyl ether, sulfolane, methyl tert-butyl ether and methyl tert-butyl ether.
According to the synthesis method of the 2-tetradecyne-1-ol, the reaction temperature of the reaction of acetylene and alkali is-20-40 ℃.
In the synthesis method of the 2-tetradecyne-1-ol, the molar ratio of the 1-bromoundecane to the alkali to the acetylene is 1: 1.1-20.
In the method for synthesizing the 2-tetradecyne-1-ol, the reaction temperature of the 1-tridecyne salt and formaldehyde is 0-60 ℃.
The synthesis method of the 2-tetradecyne-1-ol adopts paraformaldehyde for reaction.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) The invention adopts cheap and easily obtained acetylene as a starting material to react with alkali to generate acetylene salt, 1-bromoundecane is added to obtain 1-tridecyne salt, and the 1-tridecyne salt is further reacted with formaldehyde to obtain 2-tetradecyne-1-ol through synthesis by a one-pot method.
(2) The synthesis method has the advantages of low cost, mild reaction conditions, few reaction steps, short time and high purity and yield of the final product 2-tetradecyne-1-ol.
Drawings
FIG. 1 is a nuclear magnetic detection spectrum of a product 2-tetradecyne-1-ol.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
Adding 40g of powdery sodium hydroxide and 600mL of tetrahydrofuran into a reaction bottle, controlling the temperature to be about 15 ℃ under stirring, and slowly introducing dry acetylene gas, wherein the acetylene gas is stopped under the protection of a system for about 1h; controlling the temperature below 30 ℃, dropwise adding 50g of 1-bromoundecane/100 mL tetrahydrofuran solution, and continuously stirring for 5h after the dropwise adding.
Adding 30g of dry paraformaldehyde, heating to 60 ℃ and reacting for 2h; concentration to remove the solvent, addition of 250mL of water, extraction with dichloromethane 3 times, combination of the organic phases, drying, concentration, and column chromatography of the residue (eluent petroleum ether: ethyl acetate = 10: 1) to give 36g of a white solid with a purity of 99.1%, melting point: 42-43 ℃; the nuclear magnetic detection map result of the product 2-tetradecyne-1-ol is shown in figure 1. As can be seen from the view of figure 1, 1 H-NMR(400MHz，CDCl 3 )δ0.88(t，J＝8Hz，3H)，1.20-1.36(m，16H)，1.48-1.52(m，2H)，1.60(br，1H)，2.19-2.23(m，2H)，4.25(dt，J＝6.0，2.2Hz，2H)。MS(ESI[M+Na]+)：m/e[C 14 H 26 NaO]+＝233.31。
example 2
Adding 66g of powdery potassium hydroxide (85%) and 800mL of methyl tert-butyl ether into a reaction bottle, controlling the temperature to be about 15 ℃ under stirring, and slowly introducing dry acetylene gas, wherein the system is saturated for about 1h and the introduction of the acetylene gas is stopped; controlling the temperature below 35 ℃, dropwise adding 50g of 1-bromoundecane/200 mL methyl tert-butyl ether solution, and continuing stirring for 5h after the dropwise adding.
Adding 50g of dry paraformaldehyde, and heating and refluxing for reaction for 2 hours; cooling, adding 300mL of water, stirring, separating, drying the organic phase, concentrating, purifying the residue by column chromatography (eluent petroleum ether: ethyl acetate = 10: 1) to obtain 28g of white solid with purity of 98.6%, melting point: 42-44 ℃.
Example 3
Adding 1L of 1.6mol/L isopropyl magnesium bromide/tetrahydrofuran solution into a reaction bottle, cooling to 0 ℃, slowly introducing 20g of dry acetylene gas, and stirring for 1h; controlling the temperature below 20 ℃, dropwise adding 85g of 1-bromoundecane/400 mL tetrahydrofuran solution, and continuously stirring for 5h after the dropwise adding.
Controlling the temperature below 10 ℃, heating 50g of dry paraformaldehyde to 220 ℃ for decomposition, and introducing formaldehyde gas generated by decomposition into the reaction solution; heating and refluxing for 30min, cooling, concentrating to remove the solvent, adding 500mL 10% hydrochloric acid, extracting with dichloromethane for 3 times, combining the organic phases, drying, concentrating, and purifying the residue by column chromatography (eluent petroleum ether: ethyl acetate = 10: 1) to obtain 68g of white solid with purity of 99.5%, melting point: 43-44 ℃.
Example 4
Adding 20g of sodium hydrogen (60%) and 250mL of 1, 4-dioxane into a reaction bottle, slowly introducing 8g of dry acetylene gas while stirring at a temperature of about 0 ℃, and stirring for 30min; controlling the temperature below 30 ℃, dropwise adding 50g of 1-bromoundecane/100mL 1, 4-dioxane solution, and continuously stirring for 5 hours after the dropwise adding.
Controlling the temperature to be below 10 ℃, heating 15g of dry paraformaldehyde to 220 ℃ for decomposition, and introducing formaldehyde gas generated by decomposition into the reaction solution; heating to 50 deg.C for reaction for 30min, cooling, extracting with 200mL 10% hydrochloric acid and dichloromethane for 3 times, combining organic phases, drying, concentrating, and purifying with column chromatography (eluent petroleum ether: ethyl acetate = 10: 1) to obtain white solid 25g, purity 97.5%, melting point: 42-44 ℃.
Example 5
Adding 30g of potassium tert-butoxide and 250mL of sulfolane into a reaction bottle, and slowly introducing dry acetylene gas while stirring at about 15 ℃ until the system is saturated; controlling the temperature below 30 ℃, dropwise adding 1lg 1-bromoundecane/25 mL sulfolane solution, and continuously stirring for 2h after the dropwise adding is finished.
Adding 10g of dry paraformaldehyde, heating to 60 ℃ and reacting for 2h; cooling, adding 500mL water to perform extraction and quenching reaction, extracting with dichloromethane for 3 times, combining organic phases, drying, concentrating, and purifying the residue by column chromatography (eluent is petroleum ether: ethyl acetate = 10: 1) to obtain 6.8g of white solid with purity of 99.2%, melting point: 42-43 ℃.
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (3)
1. A synthetic method of 2-tetradecyne-1-alcohol is characterized in that acetylene is used as a starting material, the acetylene reacts with alkali in a solvent to generate acetylene salt, and 1-bromoundecane is added to react to obtain 1-tridecyne salt; the 1-tridecyne salt further reacts with paraformaldehyde, formaldehyde water solution or formaldehyde gas to obtain a product 2-tetradecyne-1-ol; the alkali is any one of sodium hydroxide, potassium tert-butoxide or sodium hydrogen; the solvent is one of tetrahydrofuran, methyl tetrahydrofuran, isopropyl ether, sulfolane or methyl tert-butyl ether; the method comprises the following steps:
(1) Adding alkali and a solvent into a reaction vessel, stirring and dissolving, controlling the temperature to be-20-40 ℃, introducing acetylene gas until the system is saturated, and reacting to generate acetylene salt; then dropwise adding a 1-bromoundecane solution, and after dropwise adding, controlling the temperature and stirring to react for 2-5h to generate 1-tridecyne salt; the 1-bromoundecane solution is a solution of 1-bromoundecane dissolved in the solvent, and the dosage ratio of the 1-bromoundecane to the solvent is 1-3mol; the dosage ratio of the alkali to the solvent is 1-2mol;
(2) Adding polyformaldehyde, formaldehyde aqueous solution or formaldehyde gas into the reaction solution obtained in the step (1), controlling the temperature to be 0-60 ℃, reacting for 0.5-2h, and treating the reaction solution after the reaction is finished to obtain the 2-tetradecyne-1-ol.
2. The method for synthesizing 2-tetradecyne-1-ol according to claim 1, wherein the molar ratio of 1-bromoundecane to the base to acetylene is 1.1 to 20.
3. The method of synthesizing 2-tetradecyne-1-ol according to claim 1, wherein paraformaldehyde is used for the reaction.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798293A (en) * | 2010-03-15 | 2010-08-11 | 厦门大学 | Simple stereoselective synthesis method of sex pheromones of hyphantria cunea |
| CN107556150A (en) * | 2016-06-30 | 2018-01-09 | 上海有德化工科技有限公司 | A kind of synthetic method of fall webworm sex pheromone |
| CN108299342A (en) * | 2018-01-15 | 2018-07-20 | 浙江大学 | The synthetic method of fall webworm sex pheromone intermediate |
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| CN112661725B (en) * | 2020-12-23 | 2022-11-15 | 江苏宁录科技股份有限公司 | Synthetic method of sex pheromone of fall webworm |
| CN113004223A (en) * | 2021-02-08 | 2021-06-22 | 中国农业大学 | Method for synthesizing (3Z,6Z,9S,10R) -9, 10-epoxy-3, 6-heneicosene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798293A (en) * | 2010-03-15 | 2010-08-11 | 厦门大学 | Simple stereoselective synthesis method of sex pheromones of hyphantria cunea |
| CN107556150A (en) * | 2016-06-30 | 2018-01-09 | 上海有德化工科技有限公司 | A kind of synthetic method of fall webworm sex pheromone |
| CN108299342A (en) * | 2018-01-15 | 2018-07-20 | 浙江大学 | The synthetic method of fall webworm sex pheromone intermediate |
Non-Patent Citations (1)
| Title |
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| Synthesis of linear alkynes from other alkynes;Pierre J. De Clercq等;《Science of Synthesis》;20081231;第43卷;第555页图（3） * |
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