CN1600777A - New method for picking-up alkakoid of Chinese ephedra in large scale - Google Patents
New method for picking-up alkakoid of Chinese ephedra in large scale Download PDFInfo
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- CN1600777A CN1600777A CN 03134673 CN03134673A CN1600777A CN 1600777 A CN1600777 A CN 1600777A CN 03134673 CN03134673 CN 03134673 CN 03134673 A CN03134673 A CN 03134673A CN 1600777 A CN1600777 A CN 1600777A
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- herba ephedrae
- ephedrine
- alkaloid
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Abstract
A process for extracting ephedra alkaloid including ephedrine, pseudoephedrine, methyl ephedrnie, demethyl ephedrine incldues such steps as pulverization fresh and drying ephedrine, soaking in solvent, releasing ephedrine alkaloid by outside field including microwave, ultrasonic wave, electromagnetic field etc, extracting, separating by solid mediator adsorbent, precipitation, crystallization and purifying.
Description
Technical field
The present invention relates to the production method that a kind of extensive extraction Herba Ephedrae alkaloid comprises ephedrine, pseudoephedrine, N-Methylephedrine, demethyl pseudoephedrine etc.
Background technology
Chinese ephedra has the applicating history in more than 4,000 year so far as the traditional Chinese medicine material.Medicinal kind mainly is ephedra sinica, ephedra equisetina and epheday intermedia.Mainly contain sweating, relieving asthma, Li Shui, remove the wind effect.Can control diseases such as common cold caused by wind-cold, fever with chills, lossless, Whooping cough, bronchitis, bronchial asthma.Its main effective constituent is (-) ephedrine and (+) pseudoephedrine two kinds of nitrogenous methyl Alkaloids, its structure and suprarenin similar.Since the medicine that contains PPA suspended both at home and abroad use after, ephedrine is as the best substitute of PPA, ton surplus only domestic market demand amount just has a net increase of 200, the world market annual requirement also develops into 1600 tons simultaneously.The conventional ephedrine that extracts of laboratory and hospital adopts sour water to boil formulation more at present, but extraction time is long, and extraction yield is low, and in the ephedrine production technique that enterprise adopts at present, is mostly to carry out repeatedly hot pressing adverse current digestion with hot water, and energy consumption is bigger, and the time is longer.。
The ephedrine production technique of enterprise's employing is at present carried out solvent extraction with toluene or dimethylbenzene, and toxicity is higher and solvent loss is bigger than normal.Owing to adopt repeatedly refining, decolouring, crystallization, just can obtain pure product, make the production cycle long, complex process, environmental pollution seriously and energy consumption bigger.
In addition, CN1201029A discloses a kind of new process of production that utilizes macroporous resin to prepare Ephedra sinica fine powder and byproduct tannin.This method is on existing Chinese ephedra powder extraction process basis, adds the operation that one vat liquor crossed the macropore resin bed, make the byproduct tannin be adsorbed and obtain enrichment, and other material comprises ephedrine, all through resin, is not adsorbed.Because this technology is only separated the tannin in the Chinese ephedra powder, and other impurity is not had tangible centrifugation.Therefore, the content of ephedrine only brings up to 6～10% from≤4%, and active constituent content is still very low, belongs to the Chinese ephedra meal.As seen, these class methods also exist certain defective.
Summary of the invention
The objective of the invention is to overcome the shortcoming that prior art exists, by utilizing the character of macroporous resin adsorption free state ephedrine, the generation of extracting ephedrine from the ephedrine extracting solution fast and efficiently novel process is provided, promptly provide a kind of can partly replace existing production technique and CN1201029A technology simple and easy to do, efficient, quick, cost is low and reduce the novel method of environmental pollution.
Purpose of the present invention can realize by following measure:
A kind of extensive extraction Herba Ephedrae alkaloid comprises the production method of ephedrine, pseudoephedrine, N-Methylephedrine, demethyl pseudoephedrine etc., it is characterized in that carrying out according to the following steps:
1. be 20KHz with frequency, power is that the ultrasonic of 50W ~ 10000W is being selected from water, hydrochloric acid soln to the Herba Ephedrae powder, carries out supersound extraction in the sodium hydroxide solution.
In the said extracted method, used Herba Ephedrae is a form in small, broken bits, and particle diameter is smaller or equal to 5 millimeters.
In the said extracted method, used ultrasonic time is 0.5～120 minute.
In the said extracted method, the amount of described solvent and Herba Ephedrae counts 1: 3 by weight～and 30
In the said extracted method, the used salt acid solutions is 0.0001～1N, and naoh concentration is 0.0001～1N.
2. after leach liquor being filtered, transferring pH with sodium hydroxide solution is 8 ~ 14, after the filtration, gets filtrate through weakly acidic cation-exchange resin post or macroporous resin column, and flow velocity is 0.5 ml/min～100 ml/min.
3. exchange, absorption finish, with the mixed solution wash-out of hydrochloric acid or hydrochloric acid and organic solvent, elutriant gets the ephedrine hydrochloride crystallization behind conventional concentrating under reduced pressure, eluted resins is extremely colourless with the organic solvent flushing, and with multiplexing behind 1～20 bed volume of distilled water flushing.
In above-mentioned elution process, the used salt acid concentration is 0.001～1N.
In above-mentioned elution process, used organic solvent comprises ethanol, methyl alcohol, acetone etc.The ratio of hydrochloric acid and organic solvent is 1: 0.1～10.
Below the present invention is elaborated
1. the application of ultrasonic technique in medicinal herb components extracts is to utilize cavitation effect of ultrasonic waves, can quicken effective constituent and enter solvent, increases extraction ratio of effective constituents.In addition, hyperacoustic second-order effect, as mechanical vibration, emulsification, diffusion smashes, and chemical effect also can be quickened the diffusion release that desire is extracted composition, and abundant and solvent promotes the carrying out of extracting.Microwave then is to utilize in microwave field, the difference that absorbs the microwave ability makes some zone in the Chinese medicine or some component by the heating of selectivity, thereby effective constituent is separated from Chinese medicine, enter into that specific inductivity is less, the solvent of microwave absorption capacity relative mistake.Ultrasonic technique and microwave technology be existing more application in traditional Chinese medicine ingredients is extracted
]Compare with routine techniques, it is simple that these two kinds of extractive techniques all have an operating procedure, and extraction time is short, and solvent consumption is few, the characteristics that effective component extraction rate is high.
2. ephedrine can be combined into ephedrine hydrochloride with hydrochloric acid, is dissociated into the positively charged ion state in water, and the ephedrine under this state is to be difficult to be held back with the macroporous resin that is adsorbed as main reactive force.On the other hand, macroporous resin is fine to the adsorption effect of free state ephedrine, and ephedrine is also more easily by wash-out simultaneously.
CN1201029A employing hydrochloric acid transfers pH5-8 to make ephedrine form hydrochloride, not by macroporous resin adsorption, therefore sees through resin, and this effluent liquid gets Ephedra sinica fine powder purity behind concentrate drying be 6～10%.Tannin in the extracting solution gets the byproduct tannin with ethanol elution afterwards then by macroporous resin adsorption.
And the present invention transfers pH8-14 to be controlled at free state with NaOH the ephedrine in the Herba Ephedrae extracting solution.Have only the ephedrine under this state to be adsorbed preferably by weakly acidic cation-exchange resin and macroporous resin.Afterwards, adopt the hydrochloric acid wash-out, make the free state ephedrine become ephedrine hydrochloride, not by weakly acidic cation-exchange resin and macroporous resin adsorption, thus desorb from the resin.
In the present invention, before the Herba Ephedrae extracting solution upper prop, the free state Content of Ephedrine With is about 5%, uses the hydrochloric acid wash-out behind the upper prop, and the elutriant drying under reduced pressure obtains purity and be 80% ~ 97% ephedrine hydrochloride crystallization.The salt acidifying of ephedrine and one step of wash-out finish, simply rapidly and efficiently.
3. in CN1201029A, macroporous resin adsorption tannin, make other impurity and ephedrine hydrochloride see through resin together because the decon that do not eliminate, so the Content of Ephedrine With in the gained Ephedra sinica fine powder is lower, content is 6～10%, has improved 1～2 times.
And in the present invention, hydrochloric acid only washes out ephedrine from resin, and most of lipid-soluble substance and other impurity are stayed on the resin, so ephedrine hydrochloride purity is higher, reach more than 90%, with handle before compare and improved 15～19 times.
4. in CN1201029A, how many rate of recovery of not mentioning ephedrine is, and the elution requirement that adopts in the present invention, the rate of recovery can reach 97%
5. technology of the present invention is simple, the efficient height, and weak point consuming time, cost is low and environmental pollution is little.
Be described in further detail with embodiment more below.
Embodiment
Embodiment one:
After 25 gram Herba Ephedrae are pulverized, adding 100 ml waters, is 20KHz with frequency, and power is the supersound extraction 30 minutes of 50W, removes by filter the dregs of a decoction; Regulating leach liquor pH with 0.5N NaOH is 9, with the D151 weakly acidic cation-exchange resin of filtrate by Chemical Plant of Nankai Univ.'s production.After exchange finishes, carry out wash-out, the elutriant concentrating under reduced pressure is got the ephedrine hydrochloride crystal with 0.01N hydrochloric acid; Resin column is then with can using repeatedly behind 10% alcohol flushing, but the ethanol reclaim under reduced pressure.Adopt this technology that the content 4.9% of the preceding ephedrine of sample is brought up to more than 90%, purity has improved 18.5 times, and the rate of recovery is 96%.
Embodiment two:
After 25 gram Herba Ephedrae are pulverized, adding 100 milliliters of 0.001N hydrochloric acid solns, is 20KHz with frequency, and power is the supersound extraction 30 minutes of 50W, removes by filter the dregs of a decoction; Regulating leach liquor pH with 0.5N NaOH is 14, and filtrate is passed through Rohm﹠amp; The Amberlite XAD-7 macroporous resin column of Haas company.After absorption finishes, carry out wash-out with 0.01N hydrochloric acid and 2: 1 mixing solutions of ethanol.The elutriant concentrating under reduced pressure is got the ephedrine hydrochloride crystal; Resin column is then with can using repeatedly behind 10% alcohol flushing, but the ethanol reclaim under reduced pressure.Adopt this technology that the content 5.5% of the preceding ephedrine of sample is brought up to more than 85%, purity has improved 14.8 times, and the rate of recovery is 97%.
Embodiment three:
After 25 gram Herba Ephedrae are pulverized, adding 100 milliliters of 0.005N sodium hydroxide solutions, is 20KHz with frequency, and power is the supersound extraction 30 minutes of 50W, removes by filter the dregs of a decoction; Regulating leach liquor pH with 0.5N NaOH is 10, and filtrate is passed through Rohm﹠amp; The Amberlite XAD-7 macroporous resin column of Haas company.After exchange finishes, carry out wash-out, the elutriant concentrating under reduced pressure is got the ephedrine hydrochloride crystal with 0.002N hydrochloric acid and 3: 1 mixed solution of acetone; Resin column is then with can using repeatedly behind 10% alcohol flushing, but the ethanol reclaim under reduced pressure.Adopt this technology that the content 4.1% of the preceding ephedrine of sample is brought up to more than 78%, purity has improved 18.9 times, and the rate of recovery is 95%.
Embodiment four:
After 25 gram Herba Ephedrae are pulverized, adding 100 milliliters of 0.005N sodium hydroxide solutions, is the microwave sound extraction 30 minutes of 1200W with power, removes by filter the dregs of a decoction; Regulating leach liquor pH with 0.5N NaOH is 10, and filtrate is passed through Rohm﹠amp; The Amberlite XAD-7 macroporous resin column of Haas company.After exchange finishes, carry out wash-out, the elutriant concentrating under reduced pressure is got the ephedrine hydrochloride crystal with 0.002N hydrochloric acid and 3: 1 mixed solution of acetone; Resin column is then with can using repeatedly behind 10% alcohol flushing, but the ethanol reclaim under reduced pressure.Adopt this technology that the content 4.1% of the preceding ephedrine of sample is brought up to more than 78%, purity has improved 18.9 times, and the rate of recovery is 95%.
Claims (8)
1. extensive production method of extracting Herba Ephedrae alkaloid, this method may further comprise the steps:
Fresh or exsiccant Herba Ephedrae are pulverized and solvent soaking with mechanical means, applying outfield etc. discharges Herba Ephedrae alkaloid to greatest extent from Herba Ephedrae, adjustment through potential of hydrogen is carried out, utilization utilizes extraction, membrane sepn, solid dielectric absorption to carry out alkaloidal separation, utilizes precipitated crystal to make ephedrine, pseudoephedrine, N-Methylephedrine, demethyl pseudoephedrine obtain purifying again.
2. according to the method for claim 1, wherein said mechanical means pulverizing and solvent soaking process comprise with manual or automatic knife saw cutting or with the solid particulate grinding makes Herba Ephedrae obtain pulverizing, and the mixtures a kind of or that they are two or more that add in entry, acid, alkali, salt, alcohol, alkane, the benzene soak the Herba Ephedrae after pulverizing.
3. according to the process of claim 1 wherein that said outfield comprises independent microwave field, ultrasonic wave field, electromagnetic field, perhaps they are plural uses simultaneously.
4. according to the process of claim 1 wherein that the adjustment of said potential of hydrogen comprises with various acid or alkali and the buffered soln that has an acid-basicity pH of Herba Ephedrae extract is adjusted into 1-4 or 8-14.
5. according to the process of claim 1 wherein that said extraction comprises that pH with the Herba Ephedrae extract adjusts to use after the scope of 8-14 with immiscible organic solvent such as the toluene derivative of water and contacts, make Herba Ephedrae alkaloid enter into organic solvent.
6. according to the method for claim 1, wherein said membrane sepn adopts molecular weight cut off greater than 1000 nanofiltration or ultra-filtration membrane, with the Herba Ephedrae extract with in the mode of pressure current downflow a side through film, Herba Ephedrae alkaloid sees through the opposite side that fenestra enters into film, realizes the separating of macromolecular substance such as protein, polysaccharide in Herba Ephedrae alkaloid and the Herba Ephedrae.
7. according to the process of claim 1 wherein that said solid dielectric comprises that inorganic particle, vinylbenzene-divinylbenzenes such as silica gel, aluminum oxide, diatomite are aperture, mesopore and macroporous resin or particle and derivative, sugar-containing polymer such as dextran, konjac glucomanna, agarose, chitosan microball or particle and the derivative of skeleton.
8. according to the process of claim 1 wherein that said precipitated crystal comprises the different precipitated crystals that carry out that utilize the pseudo-Chinese ephedra of ephedrine, pseudoephedrine, N-Methylephedrine, demethyl solubleness in acidic solution and organic solvent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03134673 CN1600777A (en) | 2003-09-25 | 2003-09-25 | New method for picking-up alkakoid of Chinese ephedra in large scale |
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| CN 03134673 CN1600777A (en) | 2003-09-25 | 2003-09-25 | New method for picking-up alkakoid of Chinese ephedra in large scale |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512522A (en) * | 2011-12-21 | 2012-06-27 | 江西济民可信药业有限公司 | Preparation method of children heat-cough oral liquid |
| CN103800397A (en) * | 2014-02-11 | 2014-05-21 | 浙江中医药大学 | Process for purifying Herba Ephedrae total alkaloids with macroporous resin |
| CN106588677A (en) * | 2016-11-19 | 2017-04-26 | 王丽 | Preparation method of ephedrine hydrochloride |
| CN107892652A (en) * | 2017-11-07 | 2018-04-10 | 何本科 | A kind of extracting method of ephedrine |
| CN108593634A (en) * | 2018-05-09 | 2018-09-28 | 江西德上制药股份有限公司 | The detection method of alkaloid in Chinese medicinal ingredients |
| CN110639225A (en) * | 2019-08-09 | 2020-01-03 | 唐立人 | Method for extracting alkaloid |
-
2003
- 2003-09-25 CN CN 03134673 patent/CN1600777A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512522A (en) * | 2011-12-21 | 2012-06-27 | 江西济民可信药业有限公司 | Preparation method of children heat-cough oral liquid |
| CN103800397A (en) * | 2014-02-11 | 2014-05-21 | 浙江中医药大学 | Process for purifying Herba Ephedrae total alkaloids with macroporous resin |
| CN103800397B (en) * | 2014-02-11 | 2017-06-06 | 浙江中医药大学 | The technique of macroporous resin purification Herba Ephedrae total alkaloids |
| CN106588677A (en) * | 2016-11-19 | 2017-04-26 | 王丽 | Preparation method of ephedrine hydrochloride |
| CN107892652A (en) * | 2017-11-07 | 2018-04-10 | 何本科 | A kind of extracting method of ephedrine |
| CN108593634A (en) * | 2018-05-09 | 2018-09-28 | 江西德上制药股份有限公司 | The detection method of alkaloid in Chinese medicinal ingredients |
| CN110639225A (en) * | 2019-08-09 | 2020-01-03 | 唐立人 | Method for extracting alkaloid |
| CN110639225B (en) * | 2019-08-09 | 2021-09-07 | 唐立人 | Method for extracting alkaloid |
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