A method for preparing nervonic acid monoglyceride
The synthesis of nervonic acid monoglycerides by microwave-assisted esterification and recrystallization of edible oil has solved the problems of isomerization and byproduct separation in the synthesis of nervonic acid monoglycerides, and has achieved efficient and environmentally friendly production of high-purity nervonic acid monoglycerides.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANDONG YUANLITAI MEDICAL TECH CO LTD
- Filing Date
- 2026-01-26
- Publication Date
- 2026-05-26
AI Technical Summary
Existing technologies make it difficult to synthesize nervonic acid monoglycerides efficiently, especially since nervonic acid is prone to isomerization under high temperature or strong acid and alkali conditions, and byproducts in the esterification reaction are difficult to separate and purify.
Using nervonic acid and glycerol as raw materials, an esterification reaction was carried out under microwave assistance. The mixture was then separated and purified by ethyl acetate extraction and recrystallization of edible oil, which avoided the corrosion and pollution caused by traditional acid catalysts, shortened the reaction time, and improved the synthesis efficiency.
The high-purity synthesis of nervonic acid monoglyceride was achieved, avoiding isomerization. The operation conditions were mild, making it suitable for the production of food-grade products, and it has good economic and environmental benefits.
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Figure CN122079772A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of oil and fat synthesis technology, and specifically to a method for preparing nervonic acid monoglyceride. Background Technology
[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.
[0003] Nervonic acid, first discovered in the brain tissue of mammalian sharks, is also known as squalene. Its chemical name is cis-15-tetracosenoic acid, and its molecular formula is C2. 24 H 46 O2 has a relative molecular weight of 366.6. Nervonic acid is a highly effective substance that can promote the repair and regeneration of damaged nervonic tissue. It is an important component of biological membranes and is found in high concentrations in nerve and brain tissues, serving as a natural component of brain nerve fibers and nerve cells. Nervonic acid possesses various physiological functions beneficial to the human body, including promoting the growth and development of human nerve cells and improving memory in the elderly. Furthermore, nervonic acid can repair and restore hardened and damaged cardiovascular walls, restoring vascular elasticity and vitality. With ongoing pharmacological research and analysis, nervonic acid has been widely applied in the pharmaceutical, health product, and cosmetic industries.
[0004] However, due to its high recommended intake and strong acidity, direct addition to food can easily increase the acidity of the system, affecting product stability and taste. Converting it into nervonic acid monoglycerides not only avoids acidity but also utilizes its surface-active properties to improve dispersibility and compatibility in food, pharmaceutical, and cosmetic systems.
[0005] The main methods for synthesizing fatty acid glycerides include direct esterification, epichlorohydrin esterification, and indirect esterification. Direct esterification uses fatty acids and glycerol as raw materials, reacting at 120–200 °C under acid or base catalysis. Organic solvents or vacuum conditions are often used to remove the generated water, promoting a rightward shift of the reaction equilibrium. Epichlorohydrin esterification prepares monoesters through a ring-opening addition reaction of fatty acids with epichlorohydrin; this method is mild and selective, but the raw material cost is high. Indirect esterification involves first reacting orthosilicates with glycerol to form glycerol silicate, then esterifying it with fatty acids, and finally hydrolyzing it under mild conditions to release high-purity monoglycerides. The byproduct is environmentally friendly silica.
[0006] However, the aforementioned methods are mostly applicable to the synthesis of saturated monounsaturated fatty acid glycerides. Nervonic acid, as a monounsaturated fatty acid, is prone to isomerization under high temperature or strong acid / base conditions with prolonged reaction times, generating trans fatty acids, thus affecting the structure and function of the product. Furthermore, during esterification, byproducts such as nervonic acid diglyceride and nervonic acid triglyceride are inevitably generated. Therefore, how to efficiently separate and purify the target product, mononervonic acid glyceride, from the reaction system has become a pressing problem to be solved. Summary of the Invention
[0007] To overcome the above problems, the present invention provides a method for preparing nervonic acid monoglyceride.
[0008] To achieve the above technical objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a method for preparing nervonic acid monoglyceride, comprising the following steps: (1) Using nervonic acid and glycerol as raw materials, a catalyst was added and an esterification reaction was carried out under microwave assistance to obtain the first mixture; (2) The first mixture was dispersed in a saturated sodium chloride aqueous solution, extracted with ethyl acetate, the organic phase was collected, and the solvent was removed to obtain the second mixture; (3) The second mixture was recrystallized from edible oil, and the solid was collected by filtration to obtain nervonic acid monoglyceride.
[0009] In one or more embodiments, in step (1), the molar ratio of nervonic acid to glycerol is 1:(1~5).
[0010] In one or more embodiments, in step (1), the catalyst is either zinc oxide or calcium oxide.
[0011] In one or more embodiments, in step (1), the mass ratio of the catalyst to nervonic acid is (160~200):1.
[0012] In one or more embodiments, in step (1), the microwave power is 400~700 W.
[0013] In one or more embodiments, in step (1), the esterification reaction takes 15 to 30 minutes. In one or more embodiments, in step (2), the reaction temperature is 20~25 °C.
[0014] In one or more embodiments, in step (2), the method for removing the solvent is rotary evaporation under reduced pressure.
[0015] In one or more embodiments, in step (3), the edible oil includes one or more of peanut oil, soybean oil, rapeseed oil, corn oil, sunflower seed oil, sesame oil, camellia oil or olive oil, preferably one of peanut oil, rapeseed oil or olive oil.
[0016] In one or more embodiments, in step (3), after filtering and collecting the solid, it is washed with ethanol and dried to obtain nervonic acid monoglyceride.
[0017] The beneficial effects of this invention are as follows: (1) In this invention, nervonic acid and glycerol are used as raw materials. An esterification reaction is carried out under microwave assistance to obtain a first mixture containing nervonic acid monoglyceride, nervonic acid diglyceride, nervonic acid triglyceride, unreacted nervonic acid and glycerol, and a catalyst. Glycerol and the catalyst are removed by ethyl acetate extraction to obtain a second mixture containing nervonic acid monoglyceride, nervonic acid diglyceride, nervonic acid triglyceride, and unreacted nervonic acid. Subsequently, taking advantage of the temperature-sensitive nature of nervonic acid monoglyceride in edible oil, it is separated and purified to obtain nervonic acid monoglyceride. Esterification under microwave assistance not only avoids the corrosion and pollution problems caused by traditional acid catalysts, but also significantly shortens the esterification reaction time, improves the synthesis efficiency, and effectively inhibits the isomerization of cis-nervonic acid during the reaction, ensuring the stability of the product configuration. In addition, taking advantage of the temperature-sensitive nature of nervonic acid monoglyceride in edible oil, the separation and purification of nervonic acid monoglyceride does not require the use of toxic organic solvents, the operating conditions are mild, and it is easy to promote.
[0018] (2) The raw materials used in this invention are readily available, the reaction conditions are easy to control, and the nervonic acid conversion rate is high. It not only has good economic benefits, but is also suitable for the production of food-grade products. Attached Figure Description
[0019] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.
[0020] Figure 1 The liquid phase spectrum of nervonic acid monoglyceride obtained in Example 1; Figure 2 The mass spectrum of nervonic acid monoglyceride obtained in Example 1; Figure 3 The 1H NMR spectrum of nervonic acid monoglyceride obtained in Example 1; Figure 4 The infrared spectrum of nervonic acid monoglyceride obtained in Example 1; Figure 5 The thermogravimetric spectrum of nervonic acid monoglyceride obtained in Example 1 is shown. Detailed Implementation
[0021] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.
[0022] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.
[0023] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.
[0024] The peanut oil in the following examples is from batch number Luhua DD2025 / 03 / 17, standard Q / LLH 0015S; The rapeseed oil is from batch number Luhua DF2025 / 03 / 14, standard Q / LLH 0005S; The olive oil is from the Olive Estate, batch number 2025 / 03 / 29, standard GB / T 23347-2021.
[0025] Example 1 (1) Add raw materials nervonic acid (36.6 g, 0.1 mol), glycerol (46 g, 0.5 mol) and catalyst CaO (0.2 g) to the reactor. The microwave power is 450 W. After the materials melt, start stirring and react. After reacting for 20 min, cool naturally to obtain the first mixture.
[0026] (2) At room temperature, the first mixture was dispersed in 200 g of saturated sodium chloride aqueous solution, extracted twice with 200 g of ethyl acetate, the organic phases were combined, anhydrous magnesium sulfate was added and dried, the anhydrous magnesium sulfate was removed by filtration, and the ethyl acetate was removed by rotary evaporation under reduced pressure to obtain the second mixture.
[0027] (3) The second mixture was dispersed in 200.0 g of peanut oil, heated to 80 °C to dissolve, and then cooled to 20 °C to precipitate a white solid. The solid was collected by filtration, washed with ethanol, and dried under vacuum at 30 °C to obtain nervonic acid monoglyceride (33.1 g, yield 75.1%, purity 99.1%).
[0028] Example 2 (1) Add raw materials nervonic acid (36.6 g, 0.1 mol), glycerol (27.6 g, 0.3 mol) and catalyst CaO (0.2 g) to the reactor. The microwave power is 450 W. After the materials melt, start stirring and react. After reacting for 20 min, cool naturally to obtain the first mixture.
[0029] (2) At room temperature, the first mixture was dispersed in 200 g of saturated sodium chloride aqueous solution, extracted twice with 200 g of ethyl acetate, the organic phases were combined, anhydrous magnesium sulfate was added and dried, the anhydrous magnesium sulfate was removed by filtration, and the ethyl acetate was removed by rotary evaporation under reduced pressure to obtain the second mixture.
[0030] (3) The second mixture was dispersed in 200.0 g of peanut oil, heated to 80 °C to dissolve, and then cooled to 20 °C to precipitate a white solid. The solid was collected by filtration, washed with ethanol, and dried under vacuum at 30 °C to obtain nervonic acid monoglyceride (28.8 g, yield 65.4%, purity 98.1%).
[0031] Example 3 (1) Add raw materials nervonic acid (36.6 g, 0.1 mol), glycerol (46 g, 0.5 mol) and catalyst CaO (0.2 g) to the reactor. The microwave power is 600 W. After the materials melt, start stirring and react. After reacting for 20 min, cool naturally to obtain the first mixture.
[0032] (2) At room temperature, the first mixture was dispersed in 200 g of saturated sodium chloride aqueous solution, extracted twice with 200 g of ethyl acetate, the organic phases were combined, anhydrous magnesium sulfate was added and dried, the anhydrous magnesium sulfate was removed by filtration, and the ethyl acetate was removed by rotary evaporation under reduced pressure to obtain the second mixture.
[0033] (3) The second mixture was dispersed in 200.0 g of peanut oil, heated to 80 °C to dissolve, and then cooled to 20 °C to precipitate a white solid. The solid was collected by filtration, washed with ethanol and dried under vacuum at 30 °C to obtain nervonic acid monoglyceride (28.0 g, yield 63.6%, purity 97.1%).
[0034] Example 4 (1) Add raw materials nervonic acid (36.6 g, 0.1 mol), glycerol (46 g, 0.5 mol) and catalyst ZnO (0.2 g) to the reactor. The microwave power is 450 W. After the materials melt, start stirring and react. After reacting for 20 min, cool naturally to obtain the first mixture.
[0035] (2) At room temperature, the first mixture was dispersed in 200 g of saturated sodium chloride aqueous solution, extracted twice with 200 g of ethyl acetate, the organic phases were combined, anhydrous magnesium sulfate was added and dried, the anhydrous magnesium sulfate was removed by filtration, and the ethyl acetate was removed by rotary evaporation under reduced pressure to obtain the second mixture.
[0036] (3) The second mixture was dispersed in 200.0 g of peanut oil, heated to 80 °C to dissolve, and then cooled to 20 °C to precipitate a white solid. The solid was collected by filtration, washed with ethanol, and dried under vacuum at 30 °C to obtain nervonic acid monoglyceride (32.3 g, yield 73.3%, purity 98.3%).
[0037] Example 5 (1) Add raw materials nervonic acid (36.6 g, 0.1 mol), glycerol (46 g, 0.5 mol) and catalyst CaO (0.2 g) to the reactor. The microwave power is 450 W. After the materials melt, start stirring and react. After reacting for 20 min, cool naturally to obtain the first mixture.
[0038] (2) At room temperature, the first mixture was dispersed in 200 g of saturated sodium chloride aqueous solution, extracted twice with 200 g of ethyl acetate, the organic phases were combined, anhydrous magnesium sulfate was added and dried, the anhydrous magnesium sulfate was removed by filtration, and the ethyl acetate was removed by rotary evaporation under reduced pressure to obtain the second mixture.
[0039] (3) The second mixture was dispersed in 200.0 g rapeseed oil, heated to 80 °C to dissolve, and then cooled to 20 °C to precipitate a white solid. The solid was collected by filtration, washed with ethanol and dried under vacuum at 30 °C to obtain nervonic acid monoglyceride (31.4 g, yield 71.4%, purity 98.3%).
[0040] Example 6 (1) Add raw materials nervonic acid (36.6 g, 0.1 mol), glycerol (46 g, 0.5 mol) and catalyst CaO (0.2 g) to the reactor. The microwave power is 450 W. After the materials melt, start stirring and react. After reacting for 20 min, cool naturally to obtain the first mixture.
[0041] (2) At room temperature, the first mixture was dispersed in 200 g of saturated sodium chloride aqueous solution, extracted twice with 200 g of ethyl acetate, the organic phases were combined, anhydrous magnesium sulfate was added and dried, the anhydrous magnesium sulfate was removed by filtration, and the ethyl acetate was removed by rotary evaporation under reduced pressure to obtain the second mixture.
[0042] (3) The second mixture was dispersed in 200.0 g of olive oil, heated to 80 °C to dissolve, and then cooled to 20 °C to precipitate a white solid. The solid was collected by filtration, washed with ethanol, and dried under vacuum at 30 °C to obtain nervonic acid monoglyceride (26.4 g, yield 60.1%, purity 97.2%).
[0043] Figure 1 The image shows the liquid phase spectrum of nervonic acid monoglyceride obtained in Example 1.
[0044] Figure 2 This is the mass spectrum of nervonic acid monoglyceride obtained in Example 1.
[0045] Figure 3 The image shows the 1H NMR spectrum of nervonic acid monoglyceride obtained in Example 1.
[0046] Figure 4 The infrared spectrum of nervonic acid monoglyceride obtained in Example 1.
[0047] Figure 5 The thermogravimetric spectrum of nervonic acid monoglyceride obtained in Example 1 is shown.
[0048] from Figure 1 It can be seen that the nervonic acid monoglyceride obtained by the edible oil separation method has high purity, which confirms the reliability of the method. Figure 2 The result shows that m / z = 441.3915 corresponds to the [M+H] group of nervonic acid monoglyceride. + The peak, with m / z = 423.3810, is [M-OH]. + Both peaks match the molecular formula of nervonic acid monoglyceride. Figure 3 In the ¹H NMR spectrum, the multiplet at δ = 5.36 ppm is attributed to the resonance signal of olefin hydrogen in the nervonic acid chain, and the three sets of peaks in the range of δ = 3.5-4.3 ppm correspond to the resonance signal of glycerol skeleton hydrogen. Figure 4 In the infrared spectrum, 3300 cm - The broad absorption peak at ¹ is attributed to the stretching vibration of the hydroxyl group, 1730 cm⁻¹. - The strong peak at ¹ corresponds to the stretching vibration of the ester carbonyl group, 1641 cm⁻¹. - The ¹ position represents the stretching vibration of the olefin C=C. Figure 5 Thermogravimetric analysis results showed that the product exhibited no significant weight loss below 200 °C, indicating good thermal stability and no significant water absorption. In summary, the nervonic acid monoglyceride prepared in this invention possesses typical glyceride structural characteristics and demonstrates advantages such as high purity and good thermal stability.
[0049] Verification of recrystallization mechanism: Add the nervonic acid monoglyceride prepared in Example 1 to a 100 mL Erlenmeyer flask, heat in a water bath to 50 °C, and add edible oil (peanut oil, rapeseed oil, or olive oil) dropwise to the flask while stirring continuously until the nervonic acid monoglyceride is completely dissolved in the peanut oil and the system forms a homogeneous phase. Cool to 20 °C and let stand for 24 h. Observe whether there is any precipitation or turbidity in the flask, and calculate the solubility based on the amount of peanut oil added.
[0050] Results: The solubility of nervonic acid monoglyceride in peanut oil was 0.49 g / 100g; in rapeseed oil, it was 0.68 g / 100g; and in olive oil, it was 0.89 g / 100g. This verifies that the temperature-sensitive nature of nervonic acid monoglyceride in edible oils can be utilized for separation and purification to obtain nervonic acid monoglyceride.
[0051] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A method for preparing nervonic acid monoglyceride, characterized in that, Includes the following steps: (1) Using nervonic acid and glycerol as raw materials, a catalyst was added and an esterification reaction was carried out under microwave assistance to obtain the first mixture; (2) The first mixture was dispersed in a saturated sodium chloride aqueous solution, extracted with ethyl acetate, the organic phase was collected, and the solvent was removed to obtain the second mixture; (3) The second mixture was recrystallized from edible oil, and the solid was collected by filtration to obtain nervonic acid monoglyceride.
2. The preparation method according to claim 1, characterized in that, In step (1), the molar ratio of nervonic acid to glycerol is 1:(1~5).
3. The preparation method according to claim 1, characterized in that, In step (1), the catalyst is either zinc oxide or calcium oxide.
4. The preparation method according to claim 1, characterized in that, In step (1), the mass ratio of the catalyst to nervonic acid is (160~200):
1.
5. The preparation method according to claim 1, characterized in that, In step (1), the microwave power is 400~700 W.
6. The preparation method according to claim 1, characterized in that, In step (1), the esterification reaction takes 15 to 30 minutes.
7. The preparation method according to claim 1, characterized in that, In step (2), the reaction temperature is 20~25 ℃.
8. The preparation method according to claim 1, characterized in that, In step (2), the solvent removal method is rotary evaporation under reduced pressure.
9. The preparation method according to claim 1, characterized in that, In step (3), the edible oil includes one or more of peanut oil, soybean oil, rapeseed oil, corn oil, sunflower seed oil, sesame oil, camellia oil or olive oil, preferably one of peanut oil, rapeseed oil or olive oil.
10. The preparation method according to claim 1, characterized in that, In step (3), after filtering and collecting the solid, it is washed with ethanol and dried to obtain nervonic acid monoglyceride.