CN1268597C - Preparation of pure magnolol - Google Patents
Preparation of pure magnolol Download PDFInfo
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- CN1268597C CN1268597C CN 200410012324 CN200410012324A CN1268597C CN 1268597 C CN1268597 C CN 1268597C CN 200410012324 CN200410012324 CN 200410012324 CN 200410012324 A CN200410012324 A CN 200410012324A CN 1268597 C CN1268597 C CN 1268597C
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Abstract
The present invention relates to a preparation technique of high-purity magnolol, which is characterized in that magnolia bark is crushed into grains of 55 to 65 meshes; 8 to 10mL of ethyl acetate is added to every 1g of magnolia bark; then the magnolia bark is thermally extracted at 85 to 95 DEG C for 3.8 to 4.5 hours and decompressed and concentrated into thick paste at the temperature of 40 to 50 DEG C, and the ethyl acetate is recovered; 20 to 30mL of petroleum ether required by 1g of magnolia bark thick paste is added in 4 times to an extraction flask for extraction for 4 to 5 times; extracts are merged and converted into a rotary evaporator and concentrated till extraction volume is 1/6 to 1/8 of the original volume; the concentrated extract is reversely extracted for 4 to 5 times by adding pH10.25 to pH10.75 NaOH water solution in volume 3 to 5 times of the concentrated extract, wherein the NaOH water solution is added in the volume ratio of 1:3 to 5 every time; depositions are dried in air to obtain a magnolol primary product in a content of 75 to 77%; magnolol is furthest extracted from magnolia bark into a screened extraction solvent in a hot reflux extract mode and under an optimized extract condition and concentrated with zero loss into thick paste. The present invention has low preparation cost and high product purity.
Description
Technical field
The present invention relates to the technology of preparing of medicinal plant single active ingredient, be specially a kind of high-purity magnolia bark phenol technology of preparing.
Technical background
The traditional preparation route of magnolol is with alcohols thermal backflow extracting method magnolol to be extracted from Chinese medicine web Piao, with ether or ester extraction and simmer down to medicinal extract, with column chromatography method the medicinal extract mixture is carried out purifying at last then.At present, in the magnolol technology of preparing of having reported, except conventional art or and the similar alcohol extracting of conventional art after direct column chromatography technology, comprise that also supercritical liquid extraction technique, alkali lye diacolation or alkali lye extract back abstraction purification technology.
Adopt the traditional preparation process route, the magnolol extraction yield of alcohol extracting is not very high generally at 60-70%, and purification step need be used the post isolation technique, and cost is higher when preparation of industrialization, is difficult for realizing a large amount of preparations.Employing supercritical fluid extraction route, direct extract is mixture often, and purity is not high, needs further to make with extra care, and supercritical fluid extraction equipment price costliness, once drop into too high, difficult universal.Adopt alkali lye diacolation or alkali lye to extract back abstraction purification technology, document is not reported the purity of product, just assert that by isolating result of thin-layer chromatography and result infrared, ultraviolet spectral analysis extract is exactly pure magnolol, drawn the conclusion of higher yields thus, this obviously can not be convincing.We know that the resolution of thin-layer chromatography is not high, and some kin material can not be separated thereon, and the one matter of just being assert on thin-layer chromatography as can be seen with the isolation technique of high resolution in fact might not be pure; And ultraviolet and infrared spectra can not be offered an explanation the mixture of some structure.Our similar experiment shows that only the pure substance by spectrum analysis and chromatographic separation data identification utilizes thermoanalysis technology to confirm that its purity is not very high.
Summary of the invention
Technical problem to be solved by this invention provides the technology of preparing of the mass producible magnolol that a kind of preparation cost is low, product purity is high.
The technical solution used in the present invention is as follows:
The present invention pulverizes the bark of official magnolia and is 55-65 purpose particle, the ratio that adds the 8-10mL ethyl acetate in the 1g bark of official magnolia puts it in the apparatus,Soxhlet's, 3.8-4.5h is extracted in heating under 85-95 ℃ of temperature, once for all extract, extracting solution changes rotatory evaporator over to, residue is washed once with ethyl acetate, washing lotion merges in the rotatory evaporator, concentrating under reduced pressure is thick paste and reclaims ethyl acetate under 40-50 ℃ of temperature, change thick paste over to extraction flask, thick paste in every 1g bark of official magnolia needs the ratio of 20-30mL sherwood oil to divide 4-5 time with its adding extraction flask, extract 4-5 time, combining extraction liquid changes extraction liquid over to rotatory evaporator, under 40-50 ℃ of temperature, the extraction liquid volume is concentrated into the 1/6-1/8 of original volume, changes concentrated extract over to extraction flask.Add volume 3-5 doubly to its NaOH aqueous solution reextraction 4-5 time of pH10.25-pH10.75 in concentrated extract, be 1 by volume all: the ratio of 3-5 adds this buck at every turn.Buck after merging is stripped is in other container.Add concentration and transfer pH2-3 for 2-6mol/L hydrochloric acid, mixing leaves standstill.Transfer is precipitated to other large container, and air-dry precipitation promptly gets the magnolol primary products that content reaches 75-77%.
The present invention is transferred to other container with above-mentioned air-dry precipitation magnolol primary products, and adding the 40mL volume ratio by every gram precipitation is 3-4: 1 methylene dichloride and sherwood oil mixed solvent dissolution precipitation get the recrystallization crystal, repeatedly more than 2 times in volatilizing dissolving agent process.It is 3-4 that the crystal of above-mentioned recrystallization adds the 40mL volume ratio by every gram precipitation: 1 methylene dichloride and normal hexane mixed solvent dissolution precipitation volatilize solvent recrystallization and obtain the refining magnolol that purity is 90-95%.
Positively effect of the present invention is as follows: the extraction solvent that utilization of the present invention screens to greatest extent from the bark of official magnolia extracts solvent with magnolol with the thermal backflow extracting mode under optimum extraction conditions; Make magnolol be concentrated in the thick paste and recovery extraction solvent by the concentrated condition of optimizing losslessly; The extraction solvent that utilization is selected extracts magnolol from thick paste, separate with coexisting substances such as pigments as far as possible; Concentrated extract also reclaims extraction solvent; Utilize magnolol under alkaline condition, to dissolve in water, its pKal has the principle of big gap to be stripped into magnolol in the alkaline water with the alkaline water of having optimized the pH value with Honokiol pKal and can separate with the Honokiol of coexistence as much as possible, the acidifying anti-stripping agent, magnolol is precipitated out from water and drying is obtained primary products, with appropriate solvent primary products are dissolved and recrystallization, utilize crystallisation process to separate with a small amount of coloring matter in the primary products, utilize the magnolol principle different to separate, obtain the pure product of magnolol with the Honokiol of a small amount of co-precipitation with the Honokiol crystallization rate.
Embodiment
Embodiment 1:
It is 55 purpose particles that the bark of official magnolia is pulverized, this particle diameter is for optimizing particle diameter, the ratio that adds 8mL ethyl acetate (preferred solvent) in the 1g bark of official magnolia puts it in the apparatus,Soxhlet's, 3.8h is extracted in heating under 85 ℃ of temperature, once for all extract, the extraction yield of magnolol is 80%, extracting solution changes rotatory evaporator over to, residue is washed once with ethyl acetate, and washing lotion merges in the rotatory evaporator, and concentrating under reduced pressure is thick paste and reclaims ethyl acetate under 40 ℃ of temperature, change thick paste over to extraction flask, thick paste in every 1g bark of official magnolia needs the ratio of 20mL sherwood oil to divide 4 times with its adding extraction flask, extracts combining extraction liquid 4 times, the percentage extraction of magnolol is 88%, change extraction liquid over to rotatory evaporator, under 40 ℃ of temperature, the extraction liquid volume is concentrated into 1/6 of original volume, change concentrated extract over to extraction flask.Add 3 times of volumes and strip 4 times to the NaOH of its pH10.25 aqueous solution in concentrated extract, all be that 1: 3 ratio adds this buck at every turn by volume.The pH of this aqueous solution can suppress Honokiol to greatest extent and enter water, and magnolol all is extracted into water through optimizing.Buck after merging is stripped is in other container.Add concentration and transfer pH2 for 2mol/L hydrochloric acid, mixing leaves standstill.Transfer is precipitated to other large container, air-dry precipitation, and this is the magnolol primary products, its content reaches 75%.Shift air-dry other container that is precipitated to.Adding the 40mL volume ratio by every gram precipitation is 3: 1 methylene dichloride and sherwood oil mixed solvent dissolution precipitation, must the recrystallization crystal in volatilizing dissolving agent process, and repeatedly more than 2 times.Can further separate with a small amount of Honokiol and other impurity.It is 3: 1 methylene dichloride and normal hexane mixed solvent dissolution precipitation that the crystal of above-mentioned recrystallization adds the 40mL volume ratio by every gram precipitation, volatilizes solvent recrystallization.It is 90% refining magnolol product that this crystal is purity, by primary products to the productive rate of highly finished product 50%.
Embodiment 2:
It is 65 purpose particles that the bark of official magnolia is pulverized, this particle diameter is for optimizing particle diameter, the ratio that adds 9mL ethyl acetate (preferred solvent) in the 1g bark of official magnolia puts it in the apparatus,Soxhlet's, 4.1h is extracted in heating under 95 ℃ of temperature, once for all extract, the extraction yield of magnolol is 83%, extracting solution changes rotatory evaporator over to, residue is washed once with ethyl acetate, and washing lotion merges in the rotatory evaporator, and concentrating under reduced pressure is thick paste and reclaims ethyl acetate under 45 ℃ of temperature, change thick paste over to extraction flask, thick paste in every 1g bark of official magnolia needs the ratio of 30mL sherwood oil to divide 5 times with its adding extraction flask, extracts combining extraction liquid 5 times, the percentage extraction of magnolol is 90%, change extraction liquid over to rotatory evaporator, under 50 ℃ of temperature, the extraction liquid volume is concentrated into 1/7 of original volume, change concentrated extract over to extraction flask.Add 4 times of volumes and strip 5 times to the NaOH of its pH10.50 aqueous solution in concentrated extract, all be that 1: 5 ratio adds this buck at every turn by volume.The pH of this aqueous solution can suppress Honokiol to greatest extent and enter water, and magnolol all is extracted into water through optimizing.Buck after merging is stripped is in other container.Add concentration and transfer pH3 for 4mol/L hydrochloric acid, mixing leaves standstill.Transfer is precipitated to other large container, air-dry precipitation, and this is the magnolol primary products, its content reaches 76%.Shift air-dry other container that is precipitated to.Adding the 40mL volume ratio by every gram precipitation is 4: 1 methylene dichloride and sherwood oil mixed solvent dissolution precipitation, must the recrystallization crystal in volatilizing dissolving agent process, and repeatedly more than 2 times.Can further separate with a small amount of Honokiol and other impurity.It is 4: 1 methylene dichloride and normal hexane mixed solvent dissolution precipitation that the crystal of above-mentioned recrystallization adds the 40mL volume ratio by every gram precipitation, volatilizes solvent recrystallization.It is 95% refining magnolol product that this crystal is purity, by primary products to the productive rate of highly finished product 56%.
Embodiment 3:
It is 60 purpose particles that the bark of official magnolia is pulverized, this particle diameter is for optimizing particle diameter, the ratio that adds 10mL ethyl acetate (preferred solvent) in the 1g bark of official magnolia puts it in the apparatus,Soxhlet's, 4.5h is extracted in heating under 90 ℃ of temperature, once for all extract, the extraction yield of magnolol is 82%, extracting solution changes rotatory evaporator over to, residue is washed once with ethyl acetate, and washing lotion merges in the rotatory evaporator, and concentrating under reduced pressure is thick paste and reclaims ethyl acetate under 50 ℃ of temperature, change thick paste over to extraction flask, thick paste in every 1g bark of official magnolia needs the ratio of 25mL sherwood oil to divide 4 times with its adding extraction flask, extracts combining extraction liquid 4 times, the percentage extraction of magnolol is 93%, change extraction liquid over to rotatory evaporator, under 45 ℃ of temperature, the extraction liquid volume is concentrated into 1/8 of original volume, change concentrated extract over to extraction flask.Add 5 times of volumes and strip 4 times to the NaOH of its pH10.75 aqueous solution in concentrated extract, all be that 1: 4 ratio adds this buck at every turn by volume.The pH of this aqueous solution can suppress Honokiol to greatest extent and enter water, and magnolol all is extracted into water through optimizing.Buck after merging is stripped is in other container.Add concentration and transfer pH3 for 6mol/L hydrochloric acid, mixing leaves standstill.Transfer is precipitated to other large container, air-dry precipitation, and this is the magnolol primary products, its content reaches 77%.Shift air-dry other container that is precipitated to.Adding 40mL agent volume ratio by every gram precipitation is that 3: 1 methylene dichloride mixes the broad precipitation of separating with sherwood oil, must the recrystallization crystal in volatilizing dissolving agent process, and repeatedly more than 2 times.Can further separate with a small amount of Honokiol and other impurity.It is that 3: 1 methylene dichloride adds dissolution with solvents with normal hexane mixed solvent ratio and precipitates that the crystal of above-mentioned recrystallization adds the 40mL volume ratio in every gram precipitation, volatilizes solvent recrystallization.It is 93% refining magnolol product that this crystal is purity, by primary products to the productive rate of highly finished product 53%.
Embodiment 4:
The Chinese medicine magnolia bark raw material that will contain magnolol 1.03% is crushed to 60 orders, gets 60g and places the Soxhlet extraction element, adds the 480mL ethyl acetate and extracts 4h in 90 ℃.Change extracting solution over to rotatory evaporator in 50 ℃ of simmer down to thick pastes, reclaim ethyl acetate simultaneously.Change thick paste over to extraction flask, the 240mL sherwood oil is added in the extraction flask, shift extraction liquid then, add the 240mL petroleum ether extraction again, merging is shifted in extraction, is total to total amount 1200mL 5 times repeatedly.Under 50 ℃ of temperature, the extraction liquid volume is concentrated into 1/8 of original volume, changes concentrated extract over to extraction flask again.Adding pH10.5RNaOH aqueous solution 600mL strips, and is transferred to other container then, adds same buck again and strips, and shifts to merge, and is total to total amount 3000mL 5 times repeatedly.Add 6mol/L hydrochloric acid and transfer to pH2, mixing leaves standstill.Transfer is precipitated to other large container, and is air-dry, can obtain the 0.43g throw out, and this is the magnolol primary products, and its content reaches 76%.Shift air-dry other container that is precipitated to, add 20mL methylene dichloride and sherwood oil mixed solvent, the two volume ratio is 4: 1, dissolution precipitation gets the recrystallization crystal in volatilizing dissolving agent process, this process is 2 times repeatedly, add 20mL methylene dichloride and normal hexane mixed solvent to the recrystallization crystal that obtains again, the two volume ratio is 4: 1, volatilizes solvent recrystallization, obtains purity and be 92% magnolol 0.24g.
Claims (2)
1, a kind of high-purity magnolia bark phenol technology of preparing, it is characterized in that the bark of official magnolia is pulverized is 55-65 purpose particle, the ratio that adds the 8-10mL ethyl acetate in the 1g bark of official magnolia puts it in the apparatus,Soxhlet's, 3.8-4.5h is extracted in heating under 85-95 ℃ of temperature, once for all extract, extracting solution changes rotatory evaporator over to, residue is washed once with ethyl acetate, washing lotion merges in the rotatory evaporator, concentrating under reduced pressure is thick paste and reclaims ethyl acetate under 40-50 ℃ of temperature, change thick paste over to extraction flask, thick paste in every 1g bark of official magnolia needs the ratio of 20-30mL sherwood oil to divide 4-5 time with its adding extraction flask, extract 4-5 time, combining extraction liquid, change extraction liquid over to rotatory evaporator, under 40-50 ℃ of temperature, the extraction liquid volume is concentrated into the 1/6-1/8 of original volume, change concentrated extract over to extraction flask, in concentrated extract, add volume 3-5 doubly to its NaOH aqueous solution reextraction 4-5 time of pH10.25-pH10.75, be 1 by volume all: the ratio of 3-5 adds this buck at every turn, buck after merging is stripped is in other container, add concentration and transfer pH2-3 for 2-6mo1/L hydrochloric acid, mixing leaves standstill, transfer is precipitated to other large container, air-dry precipitation promptly gets the magnolol primary products that content reaches 75-77%.
2, a kind of high-purity magnolia bark phenol technology of preparing according to claim 1, it is characterized in that above-mentioned air-dry precipitation magnolol primary products are transferred to other container, adding the 40mL volume ratio by every gram precipitation is 3-4: 1 methylene dichloride and sherwood oil mixed solvent dissolution precipitation, in volatilizing dissolving agent process, get the recrystallization crystal, repeatedly more than 2 times, it is 3-4 that the crystal of above-mentioned recrystallization adds the 40mL volume ratio by every gram precipitation: 1 methylene dichloride and normal hexane mixed solvent dissolution precipitation volatilize solvent recrystallization and obtain the refining magnolol that purity is 90-95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012324 CN1268597C (en) | 2004-06-08 | 2004-06-08 | Preparation of pure magnolol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012324 CN1268597C (en) | 2004-06-08 | 2004-06-08 | Preparation of pure magnolol |
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| CN1583700A CN1583700A (en) | 2005-02-23 |
| CN1268597C true CN1268597C (en) | 2006-08-09 |
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| CN 200410012324 Expired - Fee Related CN1268597C (en) | 2004-06-08 | 2004-06-08 | Preparation of pure magnolol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947778A (en) * | 2018-08-28 | 2018-12-07 | 北京国康本草物种生物科学技术研究院有限公司 | A method of it introducing intermediate and separates Magnolia cortex P.E |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4757911B2 (en) * | 2005-05-30 | 2011-08-24 | コリア インスティテュート オブ オリエンタル メディシン | Mass separation of magnolol from magnolia cortex or magnolia root |
| CN101857530B (en) * | 2010-05-26 | 2012-11-21 | 曾健青 | Separation method for magnolol and honokiol |
| CN102952002A (en) * | 2011-08-22 | 2013-03-06 | 冉志龙 | Method for refining magnolol through supersonic extraction separating technology |
| CN102267877A (en) * | 2011-09-05 | 2011-12-07 | 于华忠 | Method for extracting and separating magnolol and honokiol from leaf of magnolia officinalis |
| CN102977062B (en) * | 2012-11-29 | 2015-03-18 | 海南师范大学 | Magnolol compound as well as preparation method and application of magnolol compound |
| CN110934787B (en) * | 2019-11-27 | 2022-04-19 | 陈少威 | Anti-aging composition and preparation method thereof |
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2004
- 2004-06-08 CN CN 200410012324 patent/CN1268597C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947778A (en) * | 2018-08-28 | 2018-12-07 | 北京国康本草物种生物科学技术研究院有限公司 | A method of it introducing intermediate and separates Magnolia cortex P.E |
| CN108947778B (en) * | 2018-08-28 | 2021-11-05 | 北京国康本草物种生物科学技术研究院有限公司 | Method for separating magnolia bark extract by introducing intermediate |
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