CN100526329C - Production of high-purity peiminine and fritimine - Google Patents
Production of high-purity peiminine and fritimine Download PDFInfo
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- CN100526329C CN100526329C CNB2005101115450A CN200510111545A CN100526329C CN 100526329 C CN100526329 C CN 100526329C CN B2005101115450 A CNB2005101115450 A CN B2005101115450A CN 200510111545 A CN200510111545 A CN 200510111545A CN 100526329 C CN100526329 C CN 100526329C
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Abstract
Production of high-purity peiminine and fritimine by high-speed counter-current chromatogram technology is carried out by taking peimine as sampling substance, forming fixed-phase and flow-phase solvent system, pumping fixed-phase and flow-phase into column simultaneously, rotating host, sampling by sample injector, inspecting elution solvent, accepting object component and collecting to obtain the final product. The solvent system comprises chloro-alkane,fatty alcohol, aliphatic ketone and dilute acid solutions. It's cheap and convenient.
Description
Technical field
The present invention relates to a kind of preparation method of haplont alkali, relate in particular to the preparation method of a kind of high purity peimine, Peininine.
Background technology
Thunberg Fritillary Bulb is a kind of per nnial herb of Liliaceae Fritillaria, and its bulb has removing heat-phlegm, and cough-relieving is opened strongly fragrantly, and the effect of dissipating bind is used for phlegm heat cough, lung carbuncle, and acute mastitis, multiple eqpidemic disease such as subcutaneous nodule is the clinical prescription of a Chinese medicine medicine materical crude slice commonly used.Its medicine materical crude slice kind has Da Bei, pearl shellfish, three kinds of Zhejiang shellfish sheets.Effective constituent in the Thunberg Fritillary Bulb is steroid alkaloid class and glycosides thereof.Mainly contain peimine (peimine, verticine, peimine), dehydrogenation peimine (Peininine, verticinone, peiminine) and the trace the new alkali of the bulb of fritillary (peimisine), peimiphine (peimiphine), peimidine (peimidine), Peimitidine (peimitidine).In addition, still contain sterioside Alkaloid peiminoside (peiminoside), a kind of sterols neutral substance propeimine (propeimin).Alkaloid in the Thunberg Fritillary Bulb is cough-relieving, the effective constituent that reduce phlegm and relievining asthma etc. acts on, and the hydrochloride of peimine has stronger reverse effect to the resistance streptococcus aureus under finite concentration, mainly plays a role by the active efflux pump that suppresses on the bacterial cell membrane.And Recent study shows that Peininine has activity for reversing tumor cell multidrug resistance.
Structural formula is as follows:
R=α-OH, and β-H R '=H peimine (peimine, verticine, peimine)
R=O R '=H dehydrogenation peimine (Peininine, verticinone, peiminine)
R=d-OH, β-H R '=-D-glucose peiminoside (peiminoside)
From the structural formula of peimine and Peininine as can be seen: both all belong to tetrahydroisoquinoline alkaloid, have isocholestane (C
27) skeleton, contain six rings, A wherein, B, D, E, F are six-ring, C is a five-ring.Nitrogen-atoms is positioned at E, F ring junction, and both are quaternary amine alkali.
The molecular formula of peimine: C
27H
45NO
3, physicochemical characteristic: fusing point: 222-224 ℃, be dissolved in chloroform, methyl alcohol, ethanol, ethyl acetate.
The molecular formula of Peininine: C
27H
43NO
3, physicochemical characteristic: fusing point: 212-214 ℃, be dissolved in chloroform, methyl alcohol, ethanol, ethyl acetate.
Because the structure of peimine and Peininine is quite similar in the Thunberg Fritillary Bulb, adds the two content in Thunberg Fritillary Bulb very low (＜0.08%), has brought bigger difficulty to separation.Mostly the separation of traditional haplont alkali is to adopt following method: use earlier organic solvent, obtain crude extract as extraction using alcohol, contain a large amount of other impurity in this crude extract, peimine and Peininine content are all lower, crude extract also needs with the sour water dissolving, filters, and organic solvent is used in the back, as sherwood oil, ethyl acetate extraction obtains monomeric alkaloid through silica gel column chromatography.This method complicated operation, step is tediously long, and sample absorption loss is big.Zhang Jianxing etc. prepare peimine and Peininine by the method separation of column chromatography, and the rate of recovery is lower than 1%.
(High Speed Countercurrent Chromatography HSCCC) is a kind of novel liquid-liquid chromatography separation method that grows up the nineties in 20th century to high-speed countercurrent chromatography.Its principle is the centrifugal force that utilizes borded pile to produce when planetary motion, immiscible two-phase is constantly mixed, keep a phase (solid phase) wherein simultaneously, utilize constant flow pump to import another phase (moving phase) continuously, the solute that enters borded pile with moving phase distributes between two-phase repeatedly, press the order of partition ratio, quilt is wash-out successively.The elder generation that allocation proportion is big in moving phase is by wash-out, otherwise, solid mutually in big back of allocation proportion by wash-out.Be different from traditional liquid phase chromatography, the HSCCC analytical procedure is not used solid phase carrier, thereby has avoided effective constituent by shortcomings such as the irreversible adsorption of solid phase carrier and peak shape hangovers; But sample crude extract direct injection is separated, and can separate by efficient, quick and big preparation amount, and separation and purification can be finished synchronously with preparation, and organic solvent consumption is few, free of losses, pollution-free.Based on above advantage, no matter the HSCCC chromatographic instrument is as analysis mode instrument or preparation type instrument, on natural product, have wide development prospect and actual application value, it can extract the effective constituent of different qualities from the natural raw product of complexity, for the development of natural drug provides favourable condition.At present, Chinese scholars is utilized HSCCC effective constituent such as flavones, alkaloid, anthraquinone derivatives, saponin in the separation and Extraction natural drug successfully.
At present, also do not utilize HSCCC to separate effective constituent-peimine and Peininine in the Thunberg Fritillary Bulb medicine materical crude slice.
Summary of the invention
The technical problem to be solved in the present invention provides the preparation method of a kind of high purity peimine, Peininine, and it has overcome solid-state upholder or carrier irreversible adsorption, loss and sex change, and the Separation and Recovery rate is improved, and saves solvent, easy and simple to handle.
For solving the problems of the technologies described above, the preparation method of a kind of high purity peimine of the present invention, Peininine, it adopts high-speed countercurrent chromatography, may further comprise the steps: preparation Thunberg Fritillary Bulb crude extract is as the sample introduction thing; Configuration constitutes the solvent systems of stationary phase and moving phase; Stationary phase and moving phase pump in the post simultaneously; Main frame rotates, and by the sampling valve sample introduction, detects eluting solvent, and the receiving target component is collected and obtained product.Described solvent systems is chloroparaffins such as three component solvent systems, the optional chloroform of A component, tetrachloromethane; Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ketones such as the optional methyl alcohol of B component, ethanol, acetone; The C component is diluted acid solution such as dilute hydrochloric acid, dilute phosphoric acid.Preferred chloroform-ethanol-dilute hydrochloric acid solvent system.
Each component chloroparaffin of described solvent systems, Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ketone, the volume ratio of diluted acid solution is (2-6): (1-4): 2,3:2:2 for example, 4:3:2,4:1.5:2 etc., preferred 3:2:2.
The concentration of described diluted acid solution between 0.05-0.5mol/l, 0.1mol/l for example, 0.2mol/l etc.Preferred 0.2mol/l.
When described stationary phase and moving phase pumped in the post simultaneously, control stationary phase retention value was 0.4-0.8.
Engine speed and flow rate of mobile phase need be controlled in certain scope, by volume solvent system are placed separating funnel, shake up standing demix.Behind the ready to balance certain hour, will go up phase (stationary phase) and separate, adopt TBE-300A high-speed counter-current chromatograph with following (moving phase) mutually, this type column volume is 119ml, the sample introduction circle is 10ml, is furnished with AKTA purifier P-900 pump, ELSD (evaporative light scattering detection instrument).Adopt AKTA purifier P-900 double pump to pump into stationary phase and moving phase simultaneously, make it be full of whole pillar, rotate main frame then, the main control system rotating speed pumps into moving phase separately at 500-999r/min, and the control flow rate of mobile phase is at 0.5-3mL/min.Preferably: engine speed is 800r/min, and flow rate of mobile phase is 1.2mL/min.
The present invention is fit to 15-30 ℃ of temperature, and in the said temperature scope, when temperature was low, the appearance time that ELSD (evaporative light scattering detection instrument) detects slightly shifted to an earlier date, and separation efficiency changes little, and peak shape is not had much influences.
Preparation process of the present invention includes an individual system.After the peimine of collecting after the process flash liberation of system and the cut evaporate to dryness of Peininine, the chloroform dissolving,, can obtain the white solid of peimine and Peininine through washing three times.Detect through high performance liquid chromatography (HPLC), purity is all more than 95%.
The present invention has following beneficial effect: the high speed adverse current chromatogram isolation technique that the present invention adopts, be a kind of successive need not any solid support efficiently, liquid luquid partition chromatography isolation technique fast, it has overcome solid-state upholder or carrier irreversible adsorption, loss and sex change, make separated object rate of recovery height, theory reaches 100%, and the present invention is actual to be reached more than 99%.Because adopt preferred solvent system, processing condition such as controlled temperature, adjustment engine speed and flow rate of mobile phase can high efficiencyly be separated, and obtain highly purified haplont alkali (peimine, Peininine reach 98%, 95% respectively) again.And be fit to from the Thunberg Fritillary Bulb crude extract of various technology approach preparations.Guarantee higher peak shape resolution, fractional dose is big, the rate of recovery is high, isolating environment relaxes, save solvent, easy and simple to handle.
Description of drawings
Fig. 1 is that the HSCCC-ELSD of the embodiment of the invention 1 detects collection of illustrative plates;
Fig. 2 is that the HSCCC-ELSD of the embodiment of the invention 2 detects collection of illustrative plates;
Fig. 3 is that the HSCCC-ELSD of the embodiment of the invention 3 detects collection of illustrative plates;
Fig. 4 is that the HSCCC-ELSD of the embodiment of the invention 4 detects collection of illustrative plates;
Fig. 5 is that the HSCCC-ELSD of the embodiment of the invention 5 detects collection of illustrative plates.
Embodiment
The invention will be further elaborated by the following examples:
Embodiment 1:
Get Thunberg Fritillary Bulb powder (crossing 60 mesh sieves) 20g, after adding 20ml ammoniacal liquor soaks into 1h, add chloroform-methyl alcohol (4:1) mixing solutions 100ml, place 80 ℃ of heating in water bath 2h, filter, with the filtrate evaporate to dryness, residue is standby.
From system, choose chloroform-ethanol-0.2M hydrochloric acid soln and separate preparation peimine and Peininine at half countercurrent chromatography instrument.Volume ratio by 4:3:2 places separating funnel with solvent system, shakes up standing demix.Behind the ready to balance certain hour, will go up phase (stationary phase) and separate with following (moving phase) mutually.The setting experimental temperature is: 25 ℃.Adopt TBE-300A type high-speed counter-current chromatograph, column volume 119ml, sample introduction circle are 10ml, AKTA purifier P-900 pump, ELSD detector, HX-1050 constant temperature circulator.
Taking by weighing the 50mg crude extract is dissolved under the 20mL stand-by in the phase mixing solutions.Before the sample introduction, earlier stationary phase and moving phase are full of whole pillar, adjust engine speed 800r/min with AKTA purifier P-900 pump, the rotation main frame, moving phase pumps in the post with the flow velocity of 1.2mL/min, treat system stability after, by the sampling valve sample introduction.Detect collection of illustrative plates, receiving target composition according to ELSD (evaporative light scattering detection instrument) then.The HSCCC-ELSD collection of illustrative plates as shown in Figure 1, wherein, peak 3 is a Peininine, peak 5 is a peimine.Target component collects after behind the evaporate to dryness, chloroform dissolving, wash three times, can get the white solid of peimine and Peininine, and both are respectively 98% and 95% through HPLC-ELSD detection purity.And the process proton nmr spectra (
1HNRM), mass spectrum (MS) Test Identification structure.
Get Thunberg Fritillary Bulb powder (crossing 60 mesh sieves) 20g, after adding 20ml ammoniacal liquor soaks into 1h, add chloroform-methyl alcohol (4:1) mixing solutions 100ml, place 80 ℃ of heating in water bath 2h, filter, with the filtrate evaporate to dryness, residue is standby.
From system, choose chloroform-ethanol-0.1mol/l hydrochloric acid soln and separate preparation peimine and Peininine at half countercurrent chromatography instrument.Volume ratio by 2:1:2 places separating funnel with solvent system, shakes up standing demix.Behind the ready to balance certain hour, will go up phase (stationary phase) and separate with following (moving phase) mutually.The setting experimental temperature is: 25 ℃.Adopt TBE-300A type high-speed counter-current chromatograph, column volume 119ml, sample introduction circle are 10ml, AKTA purifier P-900 pump, ELSD detector, HX-1050 constant temperature circulator.
Taking by weighing the 50mg crude extract is dissolved under the 20mL stand-by in the phase mixing solutions.Before the sample introduction, earlier stationary phase and moving phase are full of whole pillar, adjust engine speed 800r/min with AKTA purifierP-900 pump, the rotation main frame, moving phase pumps in the post with the flow velocity of 1.2mL/min, treat system stability after, by the sampling valve sample introduction.Detect collection of illustrative plates, receiving target composition according to ELSD (evaporative light scattering detection instrument) then.The HSCCC-ELSD collection of illustrative plates as shown in Figure 2, wherein, peak 3 is a Peininine, peak 4 is a peimine.Target component collects after behind the evaporate to dryness, chloroform dissolving, wash three times, can get the white solid of peimine and Peininine, and both all are higher than 95% through HPLC-ELSD detection purity.And the process proton nmr spectra (
1HNRM), mass spectrum (MS) Test Identification structure.
Get Thunberg Fritillary Bulb powder (crossing 60 mesh sieves) 20g, after adding 20ml ammoniacal liquor soaks into 1h, add chloroform-methyl alcohol (4:1) mixing solutions 100ml, place 80 ℃ of heating in water bath 2h, filter, with the filtrate evaporate to dryness, residue is standby.
From system, choose chloroform-ethanol-0.2mol/l phosphoric acid solution and separate preparation peimine and Peininine at half countercurrent chromatography instrument.Volume ratio by 6:4:2 places separating funnel with solvent system, shakes up standing demix.Behind the ready to balance certain hour, will go up phase (stationary phase) and separate with following (moving phase) mutually.The setting experimental temperature is: 25 ℃.Adopt TBE-300A type high-speed counter-current chromatograph, column volume 119ml, sample introduction circle are 10ml, AKTA purifier P-900 pump, ELSD detector, HX-1050 constant temperature circulator.
Taking by weighing the 50mg crude extract is dissolved under the 20mL stand-by in the phase mixing solutions.Before the sample introduction, earlier stationary phase and moving phase are full of whole pillar, adjust engine speed 700r/min with AKTA purifierP-900 pump, the rotation main frame, moving phase pumps in the post with the flow velocity of 2mL/min, treat system stability after, by the sampling valve sample introduction.Detect collection of illustrative plates, receiving target composition according to ELSD (evaporative light scattering detection instrument) then.The HSCCC-ELSD collection of illustrative plates as shown in Figure 3, wherein, peak 3 is a Peininine, peak4 is a peimine.Target component collects after behind the evaporate to dryness, chloroform dissolving, wash three times, can get the white solid of peimine and Peininine, and both all are higher than 95% through HPLC-ELSD detection purity.And the process proton nmr spectra (
1HNRM), mass spectrum (MS) Test Identification structure.
Get Thunberg Fritillary Bulb powder (crossing 60 mesh sieves) 20g, after adding 20ml ammoniacal liquor soaks into 1h, add chloroform-methyl alcohol (4:1) mixing solutions 100ml, place 80 ℃ of heating in water bath 2h, filter, with the filtrate evaporate to dryness, residue is standby.
From system, choose tetrachloromethane-methyl alcohol-0.05mol/l phosphoric acid solution and separate preparation peimine and Peininine at half countercurrent chromatography instrument.Volume ratio by 4:3:2 places separating funnel with solvent system, shakes up standing demix.Behind the ready to balance certain hour, will go up phase (stationary phase) and separate with following (moving phase) mutually.The setting experimental temperature is: 15 ℃.Adopt TBE-300A type high-speed counter-current chromatograph, column volume 119ml, sample introduction circle are 10ml, AKTA purifier P-900 pump, ELSD detector, HX-1050 constant temperature circulator.
Taking by weighing the 50mg crude extract is dissolved under the 20mL stand-by in the phase mixing solutions.Before the sample introduction, earlier stationary phase and moving phase are full of whole pillar, adjust engine speed 500r/min with AKTA purifierP-900 pump, the rotation main frame, moving phase pumps in the post with the flow velocity of 3mL/min, treat system stability after, by the sampling valve sample introduction.Detect collection of illustrative plates, receiving target composition according to ELSD (evaporative light scattering detection instrument) then.The HSCCC-ELSD collection of illustrative plates as shown in Figure 4, wherein, peak 2 is a Peininine, peak 3 is a peimine.Target component collects after behind the evaporate to dryness, chloroform dissolving, wash three times, can get the white solid of peimine and Peininine, and both all are higher than 95% through HPLC-ELSD detection purity.And the process proton nmr spectra (
1HNRM), mass spectrum (MS) Test Identification structure.
Get Thunberg Fritillary Bulb powder (crossing 60 mesh sieves) 20g, after adding 20ml ammoniacal liquor soaks into 1h, add chloroform-methyl alcohol (4:1) mixing solutions 100ml, place 80 ℃ of heating in water bath 2h, filter, with the filtrate evaporate to dryness, residue is standby.
From system, choose chloroform-acetone-0.5mol/l hydrochloric acid soln and separate preparation peimine and Peininine at half countercurrent chromatography instrument.Volume ratio by 4:1.5:2 places separating funnel with solvent system, shakes up standing demix.Behind the ready to balance certain hour, will go up phase (stationary phase) and separate with following (moving phase) mutually.The setting experimental temperature is: 30 ℃.Adopt TBE-300A type high-speed counter-current chromatograph, column volume 119ml, sample introduction circle are 10ml, AKTA purifier P-900 pump, ELSD detector, HX-1050 constant temperature circulator.
Taking by weighing the 50mg crude extract is dissolved under the 20mL stand-by in the phase mixing solutions.Before the sample introduction, earlier stationary phase and moving phase are full of whole pillar, adjust engine speed 999r/min with AKTA purifierP-900 pump, the rotation main frame, moving phase pumps in the post with the flow velocity of 3mL/min, treat system stability after, by the sampling valve sample introduction.Detect collection of illustrative plates, receiving target composition according to ELSD (evaporative light scattering detection instrument) then.The HSCCC-ELSD collection of illustrative plates as shown in Figure 5, wherein, peak 2 is a Peininine, peak4 is a peimine.Target component collects after behind the evaporate to dryness, chloroform dissolving, wash three times, can get the white solid of peimine and Peininine, and both all are higher than 95% through HPLC-ELSD detection purity.And the process proton nmr spectra (
1HNRM), mass spectrum (MS) Test Identification structure.
Claims (9)
1. the preparation method of a high purity peimine, Peininine, it adopts high-speed countercurrent chromatography, comprises the steps: to prepare the Thunberg Fritillary Bulb crude extract as the sample introduction thing; Configuration constitutes the solvent systems of stationary phase and moving phase; Stationary phase and moving phase pump in the post simultaneously; Main frame rotates, and by the sampling valve sample introduction, detects eluting solvent, and the receiving target component is collected and obtained product; It is characterized in that: the solvent systems that is adopted is by chloroparaffin, Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ketone, the diluted acid solution composition, described chloroparaffin is chloroform or tetrachloromethane, described Fatty Alcohol(C12-C14 and C12-C18) is methyl alcohol or ethanol, described aliphatic ketone is an acetone, and described diluted acid solution is the diluted acid solution of concentration between 0.05-0.5mol/l.
2. the preparation method of high purity peimine as claimed in claim 1, Peininine is characterized in that, when described stationary phase and moving phase pumped in the post simultaneously, control stationary phase retention value was 0.4-0.8.
3. the preparation method of high purity peimine as claimed in claim 1, Peininine is characterized in that: described chloroparaffin is a chloroform, and described Fatty Alcohol(C12-C14 and C12-C18) is an ethanol, and described diluted acid solution is the dilute hydrochloric acid solution of concentration between 0.05-0.5mol/l.
4. the preparation method of high purity peimine as claimed in claim 1, Peininine is characterized in that: each component chloroparaffin of described solvent systems, and Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ketone, the volume ratio of diluted acid solution is (2-6): (1-4): 2.
5. the preparation method of high purity peimine as claimed in claim 4, Peininine is characterized in that: each component chloroparaffin of described solvent systems, and Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ketone, the volume ratio of diluted acid solution is 4:3:2.
6. the preparation method of high purity peimine as claimed in claim 1, Peininine is characterized in that: the concentration of the diluted acid solution of described concentration between 0.05-0.5mol/l is 0.2mol/l.
7. the preparation method of high purity peimine as claimed in claim 1, Peininine is characterized in that: the product that described collection obtains adopts washing three times after dissolving through evaporate to dryness, chloroform, obtains the white solid of peimine and Peininine.
8. the preparation method of high purity peimine as claimed in claim 1, Peininine is characterized in that: in the described preparation process, temperature is 15-30 ℃, and engine speed is 500-999r/min, and the flow velocity that moving phase pumps in the post is 0.5-3mL/min.
9. the preparation method of high purity peimine as claimed in claim 8, Peininine is characterized in that: described engine speed is 800r/min, and described flow rate of mobile phase is 1.2mL/min.
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| CNB2005101115450A CN100526329C (en) | 2005-12-15 | 2005-12-15 | Production of high-purity peiminine and fritimine |
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| CN102772639A (en) * | 2012-08-10 | 2012-11-14 | 宁波杰顺生物科技有限公司 | Preparation method of thunberg fritillary bulb total alkaloid extract |
| CN102772638A (en) * | 2012-08-10 | 2012-11-14 | 宁波杰顺生物科技有限公司 | Crude dry extract of thunberg fritillary bulb total alkaloids |
| CN110954644B (en) * | 2019-09-09 | 2020-10-16 | 山东琪康生物技术有限公司 | Quality control method of lung clearing powder |
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Non-Patent Citations (2)
| Title |
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| 杂交贝母生物碱成分的研究. 阮汉利等.中国中药杂志，第29卷第4期. 2004 |
| 杂交贝母生物碱成分的研究. 阮汉利等.中国中药杂志，第29卷第4期. 2004 * |
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