CN108715577B - Method for extracting high-purity isopimaric acid from pine seed oil - Google Patents
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Abstract
The invention relates to a method for extracting high-purity isopimaric acid from five-leaf pine seed oil, which comprises the following steps: A. mixing the five-leaf pine seed oil and a potassium hydroxide ethanol solution according to a volume ratio, saponifying, adding HCl into transparent filtrate, and taking upper-layer oil to obtain a mixture A; B. mixing urea and methanol, dripping the mixture A, stirring, carrying out suction filtration, and removing the inclusion compound; evaporating the filtrate to remove methanol, adding water for dilution, and adding HCl; extracting with n-hexane to obtain a mixture B; C. dissolving the mixture B in acetone, adding isobutanolamine, standing, performing suction filtration, and washing to obtain a crude product of isopimaric acid ammonium salt; then purifying with ethanol, adding ether into the purified isopimaric acid ammonium salt crystal, adding HCl aqueous solution until crystallization disappears, washing ether layer with water, evaporating to remove ether, dissolving the residue in acetone, adding water until crystallization does not increase any more, then performing suction filtration and vacuum drying to obtain isopimaric acid. The invention has the advantages of high purity of the obtained isopimaric acid, low cost and high yield.
Description
Technical Field
The invention belongs to the field of plant extracts, and particularly relates to a method for extracting high-purity isopimaric acid from pine seed oil.
Technical Field
The pimaric type resin acid is a diterpene resin acid (C) which has a methyl group and a vinyl group on a C-13 tertiary carbon atom and the intramolecular double bond is a non-conjugated independent double bond19H29COOH) mainly includes some isomers of pimaric acid, isopimaric acid, sandaracopimaric acid, etc. In particular, isopimaric acid is widely present in resins (i.e., rosins) of almost all Pinus plants, particularly rosins of various origins, and also extracted from plants such as Chamaecyparis obtusa, Juniperus chinensis, Pseudobulbus Cremastrae Seu pleiones, Torreya grandis, etc. Isopimaric acid has biological activities of resisting bacteria, inflammation, microorganisms, insects, cholesterol and cancer, and is widely applied to the fields of pesticide and medicine.
In the existing literature and patent reports at home and abroad, isopimaric acid is mostly prepared by separating rosin. Currently known methods for separating and purifying isopimaric acid include an alkali metal salt method, a direct ammonium salt precipitation method, a maleic derivatization method, a benzoquinone derivatization method, and a rectification method. Because most kinds of rosin have higher content of abietic acid type resin acid and have equivalent isomers of sandaracopimaric acid, pimaric acid and the like, the method for separating and preparing isopimaric acid by taking rosin as a source generally has the defects of low extraction rate and low product purity, and the method has complex flow, higher cost and serious pollution and is difficult to realize industrial large-scale production.
China has rich pine resources and is mainly distributed in northeast regions. Pine nut oil is oil prepared from pine nut, which is a pine fruit, and related products are mainly applied to the fields of food, medicine and health-care products. In China, the reported research on the pine seed oil is less, most of the research is mainly focused on the extraction process, the physical and chemical indexes and the determination of the fatty acid composition of the pine seed oil, and the research on extracting the isopimaric acid from the pine seed oil is not reported. Since the pine seed oil also contains more isopimaric acid, if high-purity isopimaric acid can be obtained by extracting the pine seed oil with rich resources as a raw material, the raw material source of the isopimaric acid can be expanded, and the additional value of the pine seed oil can be effectively developed.
The difference in separating isopimaric acid from different raw materials is mainly that the impurity compositions in the raw materials are different. The first consideration for preparing rosin-derived isopimaric acid is to remove the abietic acid-type resin acid with high content in rosin, while the technical key point is to separate isopimaric acid from oleic acid, linoleic acid, pinolenic acid and the like by taking pine seed oil as a source. In other words, the process of extracting and separating isopimaric acid from rosin is not suitable for the extraction of isopimaric acid from pine nut oil. Therefore, an economically feasible preparation method of the pine nut oil source isopimaric acid with high purity, high yield and high efficiency is explored, and the application of the isopimaric acid in the fields of medicine, biology and agriculture is facilitated.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the method for extracting the isopimaric acid from the five-leaf pine seed oil, and the isopimaric acid extracted by the method has higher purity and has the advantages of low production cost and high extraction yield.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for extracting high-purity isopimaric acid from the seed oil of the Pinus sylvestris is characterized by comprising the following steps:
A. mixing the five-leaf pine seed oil with a potassium hydroxide ethanol solution with the concentration of 0.5-1.0 mol/L according to the weight ratio of 1:3 to 7 by volume ratio of 65 to 75oC, under the reflux condition, maintaining stirring until oil droplets disappear to obtain saponification liquid; cooling the saponified solution to room temperature, performing suction filtration to remove unsaponifiable matters, concentrating transparent filtrate to obtain concentrated solution, adding 6mol/L HCl aqueous solution, and adjusting the pH of the concentrated solution to 2-4; taking the upper oil of the concentrated solution, and evaporating to remove the residual solvent to obtain a mixture A;
B. respectively weighing the mixture A, urea and methanol obtained in the step A according to the mass ratio of 1: 3-8: 6-12, mixing the urea and the methanol, and 65oC, stirring and refluxing to be clear and transparent, then dripping the mixture A, stirring to be uniformly mixed, and stirring at 65 DEG CoC, preserving heat and refluxing for 30-60 min; then cooling to-5 to 10oC, preserving heat, standing for 10-18 h, and then quickly performing suction filtration to remove the inclusion compound; performing rotary evaporation on the filtrate to remove methanol, then adding water with the same volume as the filtrate for dilution, adding 3mol/L HCl aqueous solution for acidification until the pH value of the system is 2-4; extracting with n-hexane, discarding the water layer, and rotary evaporating to remove n-hexane to obtain mixture B;
C. b, dissolving the mixture B obtained in the step B in acetone, slowly adding isobutanolamine in an amount which is 2-8 times of the mass of the mixture B, stirring for 1-3 h, standing after the precipitate is completely formed, performing suction filtration, washing for 3 times by using ethanol with the volume fraction of 50%, and drying to obtain a crude product of isopimaric acid ammonium salt; carrying out recrystallization purification on the crude product of the isopimaric acid ammonium salt by using an ethanol water solution with the volume fraction of 95% for 3-6 times by using a compound recrystallization method to obtain isopimaric acid ammonium salt crystals; putting the purified isopimaric acid ammonium salt crystal into a proper amount of diethyl ether, then adding 3mol/L HCl aqueous solution until the crystallization disappears, taking the diethyl ether layer, washing the diethyl ether layer to be neutral by using water, evaporating to remove the diethyl ether, dissolving the remainder in a proper amount of acetone, slowly dripping water until the crystallization does not increase any more, then carrying out suction filtration, and carrying out vacuum drying on the obtained crystals to obtain the isopimaric acid.
The purity of the isopimaric acid obtained by the invention is more than 97.8 percent, which is higher than the isopimaric acid purity of 95 percent realized by the preparation method disclosed in patent document CN 200810123831.2 & lt & gt preparation method of isopimaric acid & lt & gt. Compared with the method for extracting isopimaric acid from rosin, the method for extracting the isopimaric acid from the pine nut oil by using the pine nut oil as the raw material has the advantages of high product purity, simple process flow and low cost.
The principle of the extraction method of the invention is as follows:
the saponification reaction in the step A converts fatty acid, resin acid and corresponding esters into salts, so that the solubility of a carbohydrate substance with certain water solubility in the pine nut oil can be reduced, and the sugar substance is separated out; on the other hand, separation from unsaponifiables, such as proteins, can be achieved. After separation in step a, the mixture a mainly consists of: saturated fatty acids (palmitic acid, stearic acid), monounsaturated fatty acids (oleic acid), polyunsaturated fatty acids (linoleic acid, pinolenic acid) and resin acids.
And step B, performing primary separation on the mixture A obtained in the step A by adopting a urea inclusion method. During the crystallization process, urea molecules can form a stable crystal inclusion compound with saturated fatty acid (palmitic acid and stearic acid), monounsaturated fatty acid (oleic acid) and partial multivalent unsaturated fatty acid (linoleic acid) in the mixture A to be separated out, and the pinolenic acid and the resin acid are not easily included by the urea due to certain spatial configuration. The resin acid can be effectively separated from saturated fatty acid, oleic acid and partial linoleic acid by adopting a filtering method. After separation in step B, the impurities in mixture B are mainly a small amount of linoleic acid and a small amount of pinolenic acid.
And step C, separating and extracting the isopimaric acid in the mixture B by utilizing selective precipitation of the isopimaric acid by the isobutanolamine, so as to realize effective separation of the isopimaric acid and other resin acids.
The invention provides a method for extracting high-purity isopimaric acid from five-leaf pine seed oil, which has the following beneficial effects:
1. the method adopts a process combining a saponification method, a urea inclusion method and an ammonium salt precipitation method to sequentially remove unsaponifiable matters such as saccharides, proteins and the like, fatty acids and other types of resin acids in the Chinese pine seed oil, can effectively improve the purity of the target product isopimaric acid, and finally obtains the isopimaric acid pure product with the purity higher than 97.8 percent.
2. Compared with the method for extracting isopimaric acid from rosin, the preparation method of the isopimaric acid product from the seed oil of the five-leaf pine has the advantages of simple process flow, low production cost and high product purity.
The specific implementation mode is as follows:
the following examples are further illustrative, but do not in any way limit the scope of the invention.
Example 1: a method for extracting high-purity isopimaric acid from the seed oil of the Pinus sylvestris is characterized by comprising the following steps:
A. mixing the five-leaf pine seed oil with 0.5 mol/L potassium hydroxide ethanol solution according to the weight ratio of 1: 7 in a volume ratio of 65oC, under the reflux condition, maintaining stirring until oil droplets disappear to obtain saponification liquid; cooling the saponified solution to room temperature, performing suction filtration to remove unsaponifiable matters, concentrating transparent filtrate to obtain concentrated solution, adding 6mol/L HCl aqueous solution, and adjusting the pH of the concentrated solution to 2; taking the upper oil of the concentrated solution, and evaporating to remove the residual solvent to obtain a mixture A;
B. respectively weighing the mixture A obtained in the step A, urea and methanol according to the mass ratio of 1:3:6, mixing the urea and the methanol, and 65oC, stirring and refluxing to be clear and transparent, then dripping the mixture A, stirring to be uniformly mixed, and stirring at 65 DEG CoC, preserving heat and refluxing for 30 min; then cooled to 0oC, preserving heat, standing for 12 hours, and then quickly performing suction filtration to remove the inclusion compound; performing rotary evaporation on the filtrate to remove methanol, then adding water with the same volume as the filtrate for dilution, and then adding 3mol/L HCl aqueous solution for acidification until the pH value of the system is 2; extracting with n-hexane, discarding the water layer, and rotary evaporating to remove n-hexane to obtain mixture B;
C. b, dissolving the mixture B obtained in the step B in acetone, wherein the mass of the acetone is 4 times that of the mixture B, slowly adding isobutanolamine, the adding amount of the isobutanolamine is 20% of that of the mixture B, stirring for 1h, standing after the precipitate is completely formed, performing suction filtration, washing for 3 times by using ethanol with the volume fraction of 50%, and drying to obtain a crude product of isopimaric acid ammonium salt; carrying out recrystallization purification on the crude product of the isopimaric acid ammonium salt by using an ethanol water solution with the volume fraction of 95% for 4 times by adopting a compound recrystallization method to obtain isopimaric acid ammonium salt crystals; putting the purified isopimaric acid ammonium salt crystal into ether, adding 3mol/L HCl aqueous solution until the crystallization disappears, taking the ether layer, washing the ether layer with water to be neutral, evaporating to remove the ether, dissolving the remainder in acetone, slowly dripping water until the crystallization does not increase any more, then carrying out suction filtration, and vacuumizing and drying the obtained crystal to obtain isopimaric acid, wherein the purity of the isopimaric acid is 97.8%.
Example 2: a method for extracting high-purity isopimaric acid from the seed oil of the Pinus sylvestris is characterized by comprising the following steps:
A. mixing the five-leaf pine seed oil with 0.7 mol/L potassium hydroxide ethanol solution according to the weight ratio of 1: 4 in a volume ratio of 70oC, under the reflux condition, maintaining stirring until oil droplets disappear to obtain saponification liquid; cooling the saponified solution to room temperature, performing suction filtration to remove unsaponifiable matters, concentrating transparent filtrate to obtain concentrated solution, adding 6mol/L HCl aqueous solution, and adjusting the pH of the concentrated solution to 2.6; taking the upper oil of the concentrated solution, and evaporating to remove the residual solvent to obtain a mixture A;
B. respectively weighing the mixture A obtained in the step A, urea and methanol according to the mass ratio of 1:5:8, mixing the urea and the methanol, and 65oC, stirring and refluxing to be clear and transparent, then dripping the mixture A, stirring to be uniformly mixed, and stirring at 65 DEG CoC, preserving heat and refluxing for 40 min; then cooling to-5oC, preserving heat, standing for 10 hours, and then quickly performing suction filtration to remove the inclusion compound; performing rotary evaporation on the filtrate to remove methanol, then adding water with the same volume as the filtrate for dilution, and then adding 3mol/L HCl aqueous solution for acidification until the pH value of the system is 2.6; extracting with n-hexane, discarding the water layer, and rotary evaporating to remove n-hexane to obtain mixture B;
C. b, dissolving the mixture B obtained in the step B in acetone, slowly adding isobutanolamine in an amount which is 10% of the mass of the mixture B, stirring for 2 hours, standing after the precipitate is completely formed, performing suction filtration, washing for 3 times by using ethanol with the volume fraction of 50%, and drying to obtain a crude product of isopimaric acid ammonium salt; carrying out 5-time recrystallization purification on the crude product of the isopimaric acid ammonium salt by using an ethanol water solution with the volume fraction of 95% by adopting a compound recrystallization method to obtain isopimaric acid ammonium salt crystals; putting the purified isopimaric acid ammonium salt crystal into ether, adding 3mol/L HCl aqueous solution until the crystallization disappears, taking the ether layer, washing the ether layer with water to be neutral, evaporating to remove the ether, dissolving the remainder in acetone, slowly dripping water until the crystallization does not increase any more, then carrying out suction filtration, and vacuumizing and drying the obtained crystal to obtain isopimaric acid with the purity of 98.8%.
Example 3: a method for extracting high-purity isopimaric acid from the seed oil of the Pinus sylvestris is characterized by comprising the following steps:
A. mixing the five-leaf pine seed oil with 0.9 mol/L potassium hydroxide ethanol solution according to the weight ratio of 1:6 volume ratio of 75oC, under the reflux condition, maintaining stirring until oil droplets disappear to obtain saponification liquid; cooling the saponified solution to room temperature, performing suction filtration to remove unsaponifiable matters, concentrating transparent filtrate to obtain concentrated solution, adding 6mol/L HCl aqueous solution, and adjusting the pH of the concentrated solution to 3.4; taking the upper oil of the concentrated solution, and evaporating to remove the residual solvent to obtain a mixture A;
B. respectively weighing the mixture A obtained in the step A, urea and methanol according to the mass ratio of 1:8:12, mixing the urea and the methanol, and 65oC, stirring and refluxing to be clear and transparent, then dripping the mixture A, stirring to be uniformly mixed, and stirring at 65 DEG CoC, preserving heat and refluxing for 50 min; then cooling to 5oC, preserving heat, standing for 16 hours, and then quickly performing suction filtration to remove the inclusion compound; performing rotary evaporation on the filtrate to remove methanol, then adding water with the same volume as the filtrate for dilution, and then adding 3mol/L HCl aqueous solution for acidification until the pH value of the system is 3.4; extracting with n-hexane, discarding the water layer, and rotary evaporating to remove n-hexane to obtain mixture B;
C. b, dissolving the mixture B obtained in the step B in acetone, slowly adding isobutanolamine with the mass being 6 times that of the mixture B, stirring for 2.5 hours, standing after the precipitate is completely formed, performing suction filtration, washing for 3 times by using ethanol with the volume fraction of 50%, and drying to obtain a crude product of isopimaric acid ammonium salt; carrying out recrystallization purification on the crude product of the isopimaric acid ammonium salt by using an ethanol water solution with the volume fraction of 95% for 3 times by adopting a compound recrystallization method to obtain isopimaric acid ammonium salt crystals; putting the purified isopimaric acid ammonium salt crystal into ether, adding 3mol/L HCl aqueous solution until the crystallization disappears, taking the ether layer, washing the ether layer with water to be neutral, evaporating to remove the ether, dissolving the remainder in acetone, slowly dripping water until the crystallization does not increase any more, then carrying out suction filtration, and vacuumizing and drying the obtained crystal to obtain isopimaric acid with the purity of 98.5%.
Example 4: a method for extracting high-purity isopimaric acid from the seed oil of the Pinus sylvestris is characterized by comprising the following steps:
A. mixing the five-leaf pine seed oil with a potassium hydroxide ethanol solution with the concentration of 1.0 mol/L according to the weight ratio of 1:3 in a volume ratio of 68oC, under the reflux condition, maintaining stirring until oil droplets disappear to obtain saponification liquid; cooling the saponified solution to room temperature, performing suction filtration to remove unsaponifiable matters, concentrating transparent filtrate to obtain concentrated solution, adding 6mol/L HCl aqueous solution, and adjusting the pH of the concentrated solution to 4.0; taking the upper oil of the concentrated solution, and evaporating to remove the residual solvent to obtain a mixture A;
B. respectively weighing the mixture A obtained in the step A, urea and methanol according to the mass ratio of 1:6:10, mixing the urea and the methanol, and 65oC, stirring and refluxing to be clear and transparent, then dripping the mixture A, stirring to be uniformly mixed, and stirring at 65 DEG CoC, preserving heat and refluxing for 60 min; then cooling to 10oC, preserving heat, standing for 18 hours, and then quickly performing suction filtration to remove the inclusion compound; performing rotary evaporation on the filtrate to remove methanol, then adding water with the same volume as the filtrate for dilution, and then adding 3mol/L HCl aqueous solution for acidification until the pH value of the system is 4.0; extracting with n-hexane, discarding the water layer, and rotary evaporating to remove n-hexane to obtain mixture B;
C. b, dissolving the mixture B obtained in the step B in acetone, slowly adding the isobutanolamine with the mass being 8 times that of the mixture B, stirring for 3.0h, standing after the precipitate is completely formed, performing suction filtration, washing for 3 times by using ethanol with the volume fraction of 50%, and drying to obtain a crude product of isopimaric acid ammonium salt; carrying out 6 times of recrystallization purification on the crude product of the isopimaric acid ammonium salt by using an ethanol water solution with the volume fraction of 95 percent by adopting a compound recrystallization method to obtain isopimaric acid ammonium salt crystals; putting the purified isopimaric acid ammonium salt crystal into ether, adding 3mol/L HCl aqueous solution until the crystallization disappears, taking the ether layer, washing the ether layer with water to be neutral, evaporating to remove the ether, dissolving the remainder in acetone, slowly dripping water until the crystallization does not increase any more, then carrying out suction filtration, and vacuumizing and drying the obtained crystal to obtain isopimaric acid with the purity of 98.3%.
Claims (1)
1. A method for extracting isopimaric acid from the seed oil of the five-leaf pine is characterized by comprising the following steps:
A. mixing the five-leaf pine seed oil with a potassium hydroxide ethanol solution with the concentration of 0.5-1.0 mol/L according to the weight ratio of 1:3 to 7 by volume ratio of 65 to 75oC, under the reflux condition, maintaining stirring until oil droplets disappear to obtain saponification liquid; cooling the saponified solution to room temperature, performing suction filtration to remove unsaponifiable matters, concentrating transparent filtrate to obtain concentrated solution, adding 6mol/L HCl aqueous solution, and adjusting the pH of the concentrated solution to 2-4; taking the upper oil of the concentrated solution, and evaporating to remove the residual solvent to obtain a mixture A;
B. respectively weighing the mixture A, urea and methanol obtained in the step A according to the mass ratio of 1: 3-8: 6-12, mixing the urea and the methanol, and 65oC, stirring and refluxing to be clear and transparent, then dripping the mixture A, stirring to be uniformly mixed, and stirring at 65 DEG CoC, preserving heat and refluxing for 30-60 min; then cooling to-5 to 10oC, preserving heat, standing for 10-18 h, and then quickly performing suction filtration to remove the inclusion compound; performing rotary evaporation on the filtrate to remove methanol, then adding water with the same volume as the filtrate for dilution, adding 3mol/L HCl aqueous solution for acidification until the pH value of the system is 2-4; extracting with n-hexane, discarding the water layer, and rotary evaporating to remove n-hexane to obtain mixture B;
C. b, dissolving the mixture B obtained in the step B in acetone, slowly adding isobutanolamine in an amount which is 2-8 times of the mass of the mixture B, stirring for 1-3 h, standing after the precipitate is completely formed, performing suction filtration, washing for 3 times by using ethanol with the volume fraction of 50%, and drying to obtain a crude product of isopimaric acid ammonium salt; carrying out recrystallization purification on the crude product of the isopimaric acid ammonium salt by using an ethanol water solution with the volume fraction of 95% for 3-6 times by using a compound recrystallization method to obtain isopimaric acid ammonium salt crystals; putting the purified isopimaric acid ammonium salt crystal into a proper amount of diethyl ether, then adding 3mol/L HCl aqueous solution until the crystallization disappears, taking the diethyl ether layer, washing the diethyl ether layer to be neutral by using water, evaporating to remove the diethyl ether, dissolving the remainder in a proper amount of acetone, slowly dripping water until the crystallization does not increase any more, then carrying out suction filtration, and carrying out vacuum drying on the obtained crystals to obtain the isopimaric acid.
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| CN105175243A (en) * | 2015-07-15 | 2015-12-23 | 长春万成生物电子工程有限公司 | Method for purifying pinolenic acid from pine seed oil |
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| CN1696261A (en) * | 2005-06-25 | 2005-11-16 | 中国科学院新疆理化技术研究所 | Method for gathering jpolyunsaturated fatty acid and esterified matters oil through inclusion method of urea |
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