CN101759549A - Method for preparing hypericins - Google Patents
Method for preparing hypericins Download PDFInfo
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- CN101759549A CN101759549A CN200910234066A CN200910234066A CN101759549A CN 101759549 A CN101759549 A CN 101759549A CN 200910234066 A CN200910234066 A CN 200910234066A CN 200910234066 A CN200910234066 A CN 200910234066A CN 101759549 A CN101759549 A CN 101759549A
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- hypericin
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Abstract
The invention relates to a method for separating and purifying hypericins by adopting a macroporous resin separation technique and an alumina chromatographic technique. The method comprises the following steps of: grinding fresh hypericum perforatum L, leaching the ground hypericum perforatum L for 1 to 2 hours in saturated lime solution, adjusting a pH value to 6 to 7 by hydrochloric acid at normal temperature, and performing resin separation, segmented elution, alumina chromatography, ethanol elution and cyclohexane to obtain the finished product. The method has the advantages of simple process, little energy consumption and high-purity hypericins.
Description
Technical field:
The present invention relates to the extraction and purification process of hypericin, particularly a kind of method of using resin absorption and alumina column chromatography purifying hypericin.
Background technology:
Hypericin
Chemical name: 4,4 ', 5,5 ', 7,7 '-hexahydroxy--2,2 '-dimethyl-meta benzo dianthrone (4,4 ', 5,5 ', 7,7 '-Hexahydroxy-2,2 '-dimethyl-naphthodianthrone)
Molecular formula: C
30H
16O
8
Molecular weight: 504.43
Proterties: black-and-blue needle crystal (pyridine-contain HCl methyl alcohol), 320 ℃ of fusing points (decomposition) are soluble in pyridine or other organic amines and orange red and fluorescence redly, are insoluble to most organic solvents, dissolve in the alkaline aqueous solution.To light, oxygen, thermally labile.
Hypericin is the main active ingredient of Herba Hyperici perforati, has functions such as antiviral, anticancer, antidepressant, has been used for the treatment of depression, acquired immune deficiency syndrome (AIDS), hepatitis, cancer etc., and studies show that also in recent years can efficiently act on the H 5 N 1 avian influenza C-type virus C.
Ethanol is used in the extraction of hypericin usually, yet because the content of hypericin in Herba Hyperici perforati still quite low (0.01～0.06%), so product extraction difficulty, recovery rate and purity are not high and with high costs.Obtained by macroporous resin adsorption and inverse micelle abstraction agent extraction as hypericin in the disclosed method of Chinese patent CN1880328, extraction agent configuration trouble is unfavorable for scale operation; And for example Chinese patent CN1392130 alcohol extracting operation multiplicity is many, and terminal point is difficult for judging.
Summary of the invention:
The objective of the invention is in order to provide a kind of production technique simple, energy consumption is few, and cost is low, and hypericin purity reaches more than 25%, and yield is greater than 75%, and output is big, and the cycle is short, is easy to realize industrialized hypericin extraction process.
The object of the present invention is achieved like this:
1. water is carried: fresh Herba Hyperici perforati is pulverized, is added saturated limewater and soak and stirred 1～2 hour, filtered while hot, filtrate is cooled to room temperature, regulating pH with hydrochloric acid is 6～7, crude extract;
2. resin isolation: above-mentioned crude extract is crossed resin column and is carried out saturated absorption, and water and ethanolic soln carry out stepwise elution respectively, collects the hypericin elutriant, concentrating under reduced pressure, medicinal extract;
3. alumina column chromatography: go up chromatography column after medicinal extract and aluminum oxide mixed sample, use the ethanolic soln wash-out, must chromatographic solution;
4. recrystallization: chromatographic solution is evaporated to 1/10～1/12, leaves standstill crystallization, dissolve crystal with hexanaphthene again, recrystallization 3～5 times, promptly.
The preparation method of above-mentioned hypericin, it is characterized in that described water puies forward process: the saturated limewater consumption is 10～20 times of raw material weight, and temperature control is 40～50 ℃.
The preparation method of above-mentioned hypericin is characterized in that described resin can select LSA-5B, HPD600 or HZ-841 for use.
The preparation method of above-mentioned hypericin, the stepwise elution process that it is characterized in that described resin is as follows: earlier with 8～10 times of deionized water wash-out inorganic impurities of measuring column volumes, the back is transparent to lower column liquid with 40～60% ethanol elution, again with 4～6 times of amount column volume 80～100% ethanol elution hypericins.
The preparation method of above-mentioned hypericin is characterized in that described aluminum oxide selects neutral alumina for use.
The preparation method of above-mentioned hypericin is characterized in that the condition of described wash-out aluminum oxide: concentration 30～40% ethanol removal of impurities, and concentration 70～90% ethanol elution hypericins, the wash-out terminal point is that effluent liquid is transparent.
There is following advantage in the present invention:
1) hypericin is soluble in buck, therefore can extract hypericin more fully with liming from raw material;
2) acidifying can make inorganic solute fully liquefy, and removes in through resin absorption and water washing process, can reduce the solubleness of hypericin again, makes things convenient for resin absorption;
3) utilize hypericin to be insoluble to the character of most of organic solvents, stepwise elution can make a large amount of organic impuritys wash out prior to hypericin;
4) the hypericin height thick and, therefore polarity is very little, makes the less hypericin of former content concentrate with the non-polar solvent recrystallization, obtains the higher degree product.
Further specify the present invention below in conjunction with embodiment, but the scope of protection of present invention is not limited to following embodiment.
Embodiment:
Embodiment 1:
The fresh Herba Hyperici perforati of 20kg (hypericin content 0.028%) is pulverized, added the immersion of 200L saturated limewater and be heated to 40 ℃ of stirrings 1 hour, filtered while hot, filtrate is cooled to room temperature, and adding hydrochloric acid adjusting pH is 6.1; The SA-5B resin column that above-mentioned solution is crossed column volume 5L carries out saturated absorption, uses 40L water and capacity 40% ethanolic soln wash-out resin transparent to effluent liquid respectively, uses 50L straight alcohol wash-out hypericin elutriant again, concentrating under reduced pressure; Gained medicinal extract and neutral alumina are mixed upper prop behind the sample, and transparent to effluent liquid with 30% ethanol elution, it is transparent that 70% ethanol secondary is eluted to effluent liquid, and elutriant is evaporated to original volume 1/10 for the second time, leaves standstill crystallization; Crystal is with hexanaphthene recrystallization 3 times, finally obtains 14.7g content and be 28.8% hypericin finished product.
Embodiment 2:
The fresh Herba Hyperici perforati of 20kg (hypericin content 0.031%) is pulverized, added the immersion of 220L saturated limewater and be heated to 45 ℃ of stirrings 1.5 hours, filtered while hot, filtrate is cooled to room temperature, and adding hydrochloric acid adjusting pH is 6.6; Above-mentioned solution is crossed the HPD600 macroporous resin column of column volume 5L and is carried out saturated absorption, uses 45L water and capacity 50% ethanolic soln wash-out resin transparent to effluent liquid respectively, uses 70L90% ethanol elution hypericin elutriant again, concentrating under reduced pressure; Gained medicinal extract and neutral alumina are mixed upper prop behind the sample, and transparent to effluent liquid with 35% ethanol elution, it is transparent that 80% ethanol secondary is eluted to effluent liquid, and elutriant is evaporated to original volume 1/11 for the second time, leaves standstill crystallization; Crystal is with hexanaphthene recrystallization 4 times, finally obtains 13.5g content and be 31.8% hypericin finished product.
Embodiment 3:
The fresh Herba Hyperici perforati of 20kg (hypericin content 0.030%) is pulverized, added the immersion of 240L saturated limewater and be heated to 50 ℃ of stirrings 2 hours, filtered while hot, filtrate is cooled to room temperature, and adding hydrochloric acid adjusting pH is 7; Above-mentioned solution is crossed the HZ-841 macroporous resin column of column volume 5L and is carried out saturated absorption, uses 50L water and capacity 60% ethanolic soln wash-out resin transparent to effluent liquid respectively, uses 75L80% ethanol elution hypericin elutriant again, concentrating under reduced pressure; Gained medicinal extract and neutral alumina are mixed upper prop behind the sample, and transparent to effluent liquid with 40% ethanol elution, it is transparent that 90% ethanol secondary is eluted to effluent liquid, and elutriant is evaporated to original volume 1/12 for the second time, leaves standstill crystallization; Crystal is with hexanaphthene recrystallization 5 times, finally obtains 13.6g content and be 33.1% hypericin finished product.
Claims (6)
1. the preparation method of a hypericin is characterized in that comprising following step:
1. water is carried: fresh Herba Hyperici perforati is pulverized, is added saturated limewater and soak and stirred 1～2 hour, filtered while hot, filtrate is cooled to room temperature, regulating pH with hydrochloric acid is 6～7, crude extract;
2. resin isolation: above-mentioned crude extract is crossed resin column and is carried out saturated absorption, and water and ethanolic soln carry out stepwise elution respectively, collects the hypericin elutriant, concentrating under reduced pressure, medicinal extract;
3. alumina column chromatography: go up chromatography column after medicinal extract and aluminum oxide mixed sample, use the ethanolic soln wash-out, must chromatographic solution;
4. recrystallization: chromatographic solution is evaporated to 1/10～1/12, leaves standstill crystallization, dissolve crystal with hexanaphthene again, recrystallization 3～5 times, promptly.
2. according to the preparation method of the described hypericin of claim 1, it is characterized in that described water puies forward process: the saturated limewater consumption is 10～12 times of raw material weight, and temperature control is 40～50 ℃.
3. according to the preparation method of the described hypericin of claim 1, it is characterized in that described resin can select LSA-5B, HPD600 or HZ-841 for use.
4. according to the preparation method of the described hypericin of claim 1, the stepwise elution process that it is characterized in that described resin is as follows: earlier with 8～10 times of deionized water wash-out inorganic impurities of measuring column volumes, the back is transparent to lower column liquid with 40～60% ethanol elution, again with 10～15 times of amount column volume 80～100% ethanol elution hypericins.
5. according to the preparation method of the described hypericin of claim 1, it is characterized in that described aluminum oxide selects neutral alumina for use.
6. according to the preparation method of the described hypericin of claim 1, it is characterized in that the condition of described wash-out aluminum oxide: concentration 30～40% ethanol removal of impurities, concentration 70～90% ethanol elution hypericins, the wash-out terminal point is that effluent liquid is transparent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910234066A CN101759549A (en) | 2009-11-20 | 2009-11-20 | Method for preparing hypericins |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910234066A CN101759549A (en) | 2009-11-20 | 2009-11-20 | Method for preparing hypericins |
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| CN101759549A true CN101759549A (en) | 2010-06-30 |
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| CN200910234066A Pending CN101759549A (en) | 2009-11-20 | 2009-11-20 | Method for preparing hypericins |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079696A (en) * | 2011-01-15 | 2011-06-01 | 深圳职业技术学院 | Hypericin purifying method |
| CN102329208A (en) * | 2011-05-31 | 2012-01-25 | 苏州派腾生物医药科技有限公司 | Method for extracting chimaphilin from one-flowered wintergreen |
| CN103450000A (en) * | 2013-10-08 | 2013-12-18 | 白心亮 | Method for extracting hypericin from hyperforin perforatum |
| CN105085224A (en) * | 2015-08-31 | 2015-11-25 | 桂林三宝生物科技有限公司 | Method of extracting hypericin from hypericum perforatum |
-
2009
- 2009-11-20 CN CN200910234066A patent/CN101759549A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079696A (en) * | 2011-01-15 | 2011-06-01 | 深圳职业技术学院 | Hypericin purifying method |
| CN102079696B (en) * | 2011-01-15 | 2013-09-04 | 深圳职业技术学院 | Hypericin purifying method |
| CN102329208A (en) * | 2011-05-31 | 2012-01-25 | 苏州派腾生物医药科技有限公司 | Method for extracting chimaphilin from one-flowered wintergreen |
| CN102329208B (en) * | 2011-05-31 | 2013-09-04 | 苏州派腾生物医药科技有限公司 | Method for extracting chimaphilin from one-flowered wintergreen |
| CN103450000A (en) * | 2013-10-08 | 2013-12-18 | 白心亮 | Method for extracting hypericin from hyperforin perforatum |
| CN103450000B (en) * | 2013-10-08 | 2015-03-11 | 白心亮 | Method for extracting hypericin from hyperforin perforatum |
| CN105085224A (en) * | 2015-08-31 | 2015-11-25 | 桂林三宝生物科技有限公司 | Method of extracting hypericin from hypericum perforatum |
| CN105085224B (en) * | 2015-08-31 | 2017-08-11 | 桂林三宝生物科技有限公司 | A kind of method that hypericin is extracted from hypericum perforatum |
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Application publication date: 20100630 |