Method for separating psoralen, isopsoralen and bakuchiol from fructus psoraleae

Abstract

The invention discloses a method for separating psoralen, isopsoralen and bakuchiol from fructus psoraleae. The method comprises the following steps: a) crushing fructus psoraleae; and extracting through petroleum ether to obtain a coarse petroleum ether extractive of fructus psoraleae; b) transferring the coarse petroleum ether extractive of fructus psoraleae to a polyamide column; performing gradient elution through a mixed solution of ethyl alcohol and water; collecting target current component; and performing pressure-reduced compressing to obtain bakuchiol and a mixture of psoralen and isopsoralen; and c) transferring the mixture of psoralen and isopsoralen to a silicagel column; eluting with a mixed solution of petroleum ether and ethyl acetate; collecting the target current component; and performing pressure-reduced concentration to obtain psoralen and isopsoralen. With the adoption of the method, psoralen, isopsoralen and bakuchiol can be synchronously massively separated, andthe purity is beyond 99%; the problem of synchronously separating psoralen, isopsoralen and bakuchiol can be solved.

Description

technical field [0001] The invention relates to a method for separating psoralen, isopsoralen and bakuchiol from psoralen, and belongs to the technical field of separation and purification of natural products. Background technique [0002] Psoralen is the dried and mature fruit of Psoralea corylifolia L., a leguminous plant, also known as Poguzhi, Poguzhi, and Hujiuzi. It was first seen in "Kaibao Materia Medica", and it is distributed in Shanxi, Shaanxi, Anhui and other places , has the effects of warming the kidney and helping yang, invigorating qi and relieving asthma, warming the spleen and stopping diarrhea. Modern chemical research shows that psoralen mainly contains glycosides, coumarins, flavonoids, and monoterpene phenolic components, which have antibacterial, antioxidative, antiviral, antitumor, and immune-enhancing activities. [0003] Psoralen (Psoralen, CAS#: 66-97-7, molecular formula C 11 h 6 o 3 , molecular weight is 186), isopsoralen (Isopsoralen, CAS#: ...

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Problems solved by technology

However, the HPLC method not only has a small amount of preparation, it is difficult to achieve a large amount of separation and purification, and the cost of the instrument is high; although the cost of the instrument for silica gel column purification is low, the sample is easily lost in the separation process, and the yield is low. Due to the problem of the intersection of components such as isopsoralen and psoralen B, the purity of bakuchiol obtained is relatively low, and repeated purification is required to make up for this defect, for example: disclosed in Chinese patent CN201510594624.5 A kind of preparation method of bakuchiol extract is proposed, first extract psoralen medicinal material by petroleum ether, obtain psoralen extract, extract through silica gel column chromatography once, obtain bakuchiol crude product (purity 30%), in order to improve the purity of bakuchiol, the crude product of gained bakuchiol needs to go through silica gel column chromatography again, just can obtain the pure product of bakuchiol with purity greater than 98%, although obtained the high-purity psoralen Fatty phenol, but in the separation process, due to the irreversible adsorption of silica gel to the sample, the method needs to be separated by silica gel column chromatography repeatedly, the sample is easily lost and the cycle is relatively long, and the operation is cumbersome; the operation of macroporous resin is complicated, for example: Chinese patent CN200910079502. 7. In 200910084832.5, bakuchiol was obtained by ethanol extraction, water precipitation, macroporous resin purification of the filtrate, organic solvent extraction, discarding of the extract, and washing of the residue to obtain bakuchiol. Although it can be separated in large quantities, the purity of the obtained product can reach More than 90%, but in order to separate bakuchiol from psoralen and isopsoralen and improve the purity of bakuchiol, separation and purification steps such as water extraction and alcohol precipitation, macroporous resin purification and organic solvent extraction are required , the process is complex and not suitable for mass production

[0007] Psoralen and isopsoralen belong to lactone substances, which are unstable under alkaline conditions and are easy to open rings to form salts. Therefore, some researchers use organic solvents to extract the crude psoralen extract, and then extract the crude The extract is dissolved in alkaline aqueous solution, and finally purified by column chromatography or macroporous resin, thereby separating and purifying bakuchiol. For example, the composition of bakuchiol and its preparation method are disclosed in CN200680024989.3. In the method, by alkaline water treatment, the psoralen and isopsoralen in the extract are ring-opened to form a salt, separated from bakuchiol, and then the mixture from which the psoralen and isopsoralen have been removed is passed through a column Purification by chromatography, although the separation of bakuchiol, psoralen and isopsoralen is achieved, the process is complicated, the pH needs to be adjusted, and the crude extract containing bakuchiol is exposed to strong alkali for a long time. The loss of bakuchiol in the raw material will be caused in the active system, and the yield of the obtained bakuchiol is relatively low. Although the purity of the obtained bakuchiol is in the range of 27% to 100%, in fact, in most cases, the obtained The purity of bakuchiol is relatively low. In order to obtain high-purity bakuchiol, it is unavoidable to need repeated column chromatography purification, complicated operation and long cycle; Chinese patents CN200810182713.9, CN201510887523.7 and literature ( D101 Study on enrichment of bakuchiol in psoralen by macroporous adsorption resin; Liu Erwei, Wang Jialong, Han Lifeng; Journal of Tianjin University of Traditional Chinese Medicine; Vol. 31, No. 2, pp. 95-97; June 2012) All have reported the separation and purification method of bakuchiol respectively, all are to extract psoralen with ethanol earlier, the extract that obtains is dissolved in alkaline aqueous solution, purifies with macroporous resin at last, although macroporous resin is compared with column chromatography In other words, the amount of separation is relatively large, but the separation method is still complicated in technology, needs to adjust the pH value, and still has the problem of loss of bakuchiol in the raw material caused by a strong alkaline system, and the purity of the obtained bakuchiol is also relatively low. For example: the purity of bakuchiol obtained in CN200810182713.9 is only 40-90%, and contains 2-10% psoralen flavonoids; the purity of bakuchiol obtained in CN201510887523.7 is 80% About; the purity of bakuchiol obtained in the literature is about 45.6%

[0008] In addition, when separating bakuchiol, psoralen and isopsoralen from psoralen at present, usually after targeted enrichment of bakuchiol, the remaining part is often discarded, resulting in Waste of resources, for example: CN200680024989.3, CN200810182713.9, CN201510887523.7, etc. are treated with alkaline water of psoralen extract, usually the psoralen and isopsoralen in the extract are ring-opened and salted Discard in the alkaline aqueous solution, and if avoid resource waste, just need add acid again to the alkaline aqueous solution that contains psoralen and different psoralen to adjust the psoralen salt in the solution and different psoralen salt Re-closing the ring to form a lactone, then extracting the psoralen and isopsoralen in the solution with an organic solvent, and then purifying, the operation is more complicated and not suitable for large-scale production

[0009] In summary: so far there is no method that is simple to operate and can separate high-purity psoralen, isopsoralen and bakuchiol in large quantities at the same time, so that it affects the quality of psoralen and isopsoralen. Development and utilization of medicinal value of bakuchiol

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