CN102040557A - Extracting method of laurotetanine - Google Patents

Extracting method of laurotetanine Download PDF

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Publication number
CN102040557A
CN102040557A CN201010293245XA CN201010293245A CN102040557A CN 102040557 A CN102040557 A CN 102040557A CN 201010293245X A CN201010293245X A CN 201010293245XA CN 201010293245 A CN201010293245 A CN 201010293245A CN 102040557 A CN102040557 A CN 102040557A
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China
Prior art keywords
laurotetanine
extraction
extracting method
methanol
temperature
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CN201010293245XA
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Chinese (zh)
Inventor
刘东锋
郭琴
杨成东
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Nanjing Zelang Medical Technology Co Ltd
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Nanjing Zelang Medical Technology Co Ltd
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Priority to CN201010293245XA priority Critical patent/CN102040557A/en
Publication of CN102040557A publication Critical patent/CN102040557A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Medicines Containing Plant Substances (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

The invention relates to an extracting method of laurotetanine, comprising the following steps of: with a lindera angustifolia root or a mountain spicy tree root and rhizome which is rich in the laurotetanine as a raw material, crushing to 40-80 meshes; carrying out supercritical extraction for 0.5-3 hours by taking CO2 as an extraction medium and low-carbon alcohol as an entrainer; adding cation exchange resins to a resolved material; eluting by using ammonia water; carrying out column chromatography on alumina contained in an eluent; carrying out gradient elution on a dichloromethane and methanol mixed solvent; collecting high-concentration fractions, and concentrating and crystallizing to obtain high-purity laurotetanine crystals. The invention has the advantages of high extraction efficiency, simple process, low cost, and the like.

Description

A kind of extracting method of laurotetanine
Technical field:
The invention belongs to the extracted form natural plant field, relate to a kind of extracting method of laurotetanine, especially a kind of method that adopts supercritical fluid extraction and alumina column chromatography purifying laurotetanine.
Background technology:
Laurotetanine (Laurotetanine) has another name called Litsoeine, laurotetanine; It is a kind of aporphine alkaloid.
Molecular formula: C 19H 21NO 4Molecular weight: 327.38.
Physico-chemical property: light brown crystallization, mp.124 ℃ (acetone), [α] 32/D+125 ° (chloroform); [α] 22/D+100 ° (c=0.12, ethanol).
Laurotetanine is at Lauraceae Litsea plant Tetranthera citrata (Litsea cubeba (Lour.) Pers) and Lindera plant Twig and leaf of Narrowleaf Spicebush (Lindera angustifolia Cheng).Pharmacological research shows that it has antitumor synergy, can improve the antimitotic effect of colchicine; Antiplatelet aggregative activity, when 100 μ g/mL, gathering is strong restraining effect to ADP inductive rabbit platelet; Hypotensive effect, this product produce hypotensive activity to normotensive rat when 1.0mg/kg, on average reduce by 29.0%, and continue 2 minutes; Lax blood vessel function.When this product 100 μ g/mL, powerful inhibition rat is shunk by the aorta that high K+ (80mM) and norepinephrine (3 μ M) cause.
The extracting method of laurotetanine has:
1) people such as Masao adopts extraction using alcohol, use 3% acetic acid extraction again, be concentrated into certain volume and place night filtration, the greenery chloroform extraction, acid mother liquid is neutralized to ammonium hydroxide and separates out solid after extracting, come out with chloroform extraction, extracting solution extracts with 2% sodium hydroxide solution jolting again, sodium hydroxide extraction liquid wherein adds volatile salt to separating out crystallization, uses chloroform extraction again, obtains residue with the Anhydrous potassium carbonate drying, the acetone soln of residue adds picrolonate and gets red crystallization, this method complex operation, acid-base reaction repeatedly, recrystallization, the target product loss is big in the process.
2) Chinese patent (application number 200710040166.6), use extraction using alcohol, the ethanol extraction n-butanol extraction, n-butanol extraction is partly used the silicagel column rough segmentation once, get the laurotetanine mixture, prepare the high purity laurotetanine with high-speed countercurrent chromatography again, though this method is than method 1) the separation condition gentleness, but preparation amount is very little, and cost is higher.
Summary of the invention:
The technical problem to be solved in the present invention provides a kind of extracting method of laurotetanine.This technology can reduce production costs, and improves yield.
Extractive technique scheme of the present invention is as follows:
A kind of extracting method of laurotetanine is characterized in that comprising following steps:
A. supercritical CO 2Extraction: will be rich in the pulverizing medicinal materials 40-80 order of laurotetanine, drop in the extraction kettle, and after the warming apparatus works better, open compression pump and be pressurized to 22.5-36.8MPa, extraction temperature 30-60 ℃, pumping liquid CO 2And entrainment agent, keeping above-mentioned pressure and temperature 0.5-3 hour, separating still is at pressure 6.8-14.7MPa, and extract is collected in temperature 40-60 ℃ of decompression parsing separation down;
B. ion-exchange: the said extracted thing is added Zeo-karb, 2-8% ammoniacal liquor wash-out, following fluid injection concentrate drying;
C. column chromatography purification: above-mentioned dry thing is dissolved with minimum of chloroform, add alumina chromatographic column, methylene chloride-methanol mixed solvent wash-out, collect laurotetanine high-content wash-out part, reclaim reagent, under cold condition, leave standstill growing the grain to beginning crystallization, filter, be drying to obtain product.
CO described in the step a. 2Flow control is 26-33kg/h, and entrainment agent is ethanol or methyl alcohol, consumption 2-5%.
Zeo-karb described in the step b. is strongly acidic styrene type cation exchange resin 001 * 8, macropore weak acid acrylic acid type cation exchange resin D152, weakly acidic cationic exchanger resin 724 or 732.
Aluminum oxide described in the step c is a 100-200 purpose alkali alumina, and gradient elution is 2-4BV methyl alcohol → 4-6BV methylene chloride-methanol (1: 1) mixing solutions → 3-8BV methylene chloride-methanol (1: 9) mixing solutions.
The condition of growing the grain described in the step c: temperature 4-10 ℃, rearing crystal time is 16-48h.
In sum, the present invention adopts supercritical CO 2Extraction, extraction yield height, production safety; The alumina column chromatography applied sample amount is big, and elute effect is good, the product purity height.
Further specify the present invention below in conjunction with embodiment, but the scope of the protection that the present invention requires is not limited to following embodiment.
Embodiment:
Embodiment 1:
Get 80 order Root of Mountain Spicy Tree 1kg and place extraction kettle, sealing will be extracted temperature and be transferred to 45 ℃, and the knockout tower temperature transfers to 55 ℃, extract pressure 28.3Mpa, and parsing pressure is 7.5Mpa, CO 2Gas is emitted from steel cylinder, through behind the gas purifier in liquefied pot, liquefaction, enter storage tank with high-pressure metering pump with CO 2Send into cleaner, to assigned temperature and pressure, flow velocity 30kg/h opens relief valve by preheater, by relief valve control above-mentioned parameter, dynamic extraction 2.5 hours.Emit extract after the shutdown; collect extract 88g; add 001 * Final 8 acidic cation-exchange resin post; 3% ammoniacal liquor wash-out; collecting down, the fluid injection concentrating under reduced pressure becomes medicinal extract; add the chloroform dissolving, filtrate pumps into alumina column, earlier with 3BV methanol solution wash-out impurity; use methylene chloride-methanol (1: 1), methylene chloride-methanol (1: 9) wash-out again; high Liquid Detection is collected the high density flow point, reclaims reagent to beginning crystallization; be placed on growing the grain 18h in 5 ℃ of environment; filtering crystallisate, cryodrying get laurotetanine 1.3g, content 97.5%.
Embodiment 2:
Get 40 order Twig and leaf of Narrowleaf Spicebush root 1kg and place extraction kettle, sealing will be extracted temperature and be transferred to 47 ℃, and the knockout tower temperature transfers to 59 ℃, extract pressure 26.4Mpa, and parsing pressure is 9Mpa, CO 2Gas is emitted from steel cylinder, through behind the gas purifier in liquefied pot, liquefaction, enter storage tank with high-pressure metering pump with CO 2Send into cleaner, to assigned temperature and pressure, flow velocity 28kg/h opens relief valve by preheater, by relief valve control above-mentioned parameter, dynamic extraction 2 hours.Emit extract after the shutdown; collect extract 90g; add D152 macropore weakly acidic cation-exchange resin post; 2% ammoniacal liquor wash-out; collecting down, the fluid injection concentrating under reduced pressure becomes medicinal extract; add the chloroform dissolving, filtrate pumps into alumina column, earlier with 2BV methanol solution wash-out impurity; use methylene chloride-methanol (1: 1), methylene chloride-methanol (1: 9) wash-out again; high Liquid Detection is collected the high density flow point, reclaims reagent to beginning crystallization; be placed on growing the grain 20h in 4 ℃ of environment; filtering crystallisate, cryodrying get laurotetanine 1.2g, content 98.7%.
Embodiment 3:
Get 60 order Root of Mountain Spicy Tree 5kg and place extraction kettle, sealing will be extracted temperature and be transferred to 55 ℃, and the knockout tower temperature transfers to 60 ℃, extract pressure 35.5Mpa, and parsing pressure is 10.1Mpa, CO 2Gas is emitted from steel cylinder, through behind the gas purifier in liquefied pot, liquefaction, enter storage tank with high-pressure metering pump with CO 2Send into cleaner, to assigned temperature and pressure, flow velocity 26kg/h opens relief valve by preheater, by relief valve control above-mentioned parameter, dynamic extraction 1.5 hours.Emit extract after the shutdown; collect extract 450g; add 724 weakly acidic cation-exchange resin posts; 5% ammoniacal liquor wash-out; collecting down, the fluid injection concentrating under reduced pressure becomes medicinal extract; add the chloroform dissolving, filtrate pumps into alumina column, earlier with 3BV methanol solution wash-out impurity; use methylene chloride-methanol (1: 1), methylene chloride-methanol (1: 9) wash-out again; high Liquid Detection is collected the high density flow point, reclaims reagent to beginning crystallization; be placed on growing the grain 16h in 8 ℃ of environment; filtering crystallisate, cryodrying get laurotetanine 6.5g, content 98.6%.
Embodiment 4:
Get 80 order Twig and leaf of Narrowleaf Spicebush root 10kg and place extraction kettle, sealing will be extracted temperature and be transferred to 42 ℃, and the knockout tower temperature transfers to 56 ℃, extract pressure 27.8Mpa, and parsing pressure is 12.7Mpa, CO 2Gas is emitted from steel cylinder, through behind the gas purifier in liquefied pot, liquefaction, enter storage tank with high-pressure metering pump with CO 2Send into cleaner, to assigned temperature and pressure, flow velocity 32kg/h opens relief valve by preheater, by relief valve control above-mentioned parameter, dynamic extraction 2.0 hours.Emit extract after the shutdown; collect extract 920g; add 732 weakly acidic cation-exchange resin posts; 6% ammoniacal liquor wash-out; collecting down, the fluid injection concentrating under reduced pressure becomes medicinal extract; add the chloroform dissolving, filtrate pumps into alumina column, earlier with 2BV methanol solution wash-out impurity; use methylene chloride-methanol (1: 1), methylene chloride-methanol (1: 9) wash-out again; high Liquid Detection is collected the high density flow point, reclaims reagent to beginning crystallization; be placed on growing the grain 24h in 6 ℃ of environment; filtering crystallisate, cryodrying get laurotetanine 12g, content 98.4%.
Embodiment 5:
Get 80 order Twig and leaf of Narrowleaf Spicebush root 20kg and place extraction kettle, sealing will be extracted temperature and be transferred to 45 ℃, and the knockout tower temperature transfers to 55 ℃, extract pressure 32.6Mpa, and parsing pressure is 14.7Mpa, CO 2Gas is emitted from steel cylinder, through behind the gas purifier in liquefied pot, liquefaction, enter storage tank with high-pressure metering pump with CO 2Send into cleaner, to assigned temperature and pressure, flow velocity 33kg/h opens relief valve by preheater, by relief valve control above-mentioned parameter, dynamic extraction 2.5 hours.Emit extract after the shutdown; collect extract 1.8kg; add 724 weakly acidic cation-exchange resin posts; 8% ammoniacal liquor wash-out; collecting down, the fluid injection concentrating under reduced pressure becomes medicinal extract; add the chloroform dissolving, filtrate pumps into alumina column, earlier with 3BV methanol solution wash-out impurity; use methylene chloride-methanol (1: 1), methylene chloride-methanol (1: 9) wash-out again; high Liquid Detection is collected the high density flow point, reclaims reagent to beginning crystallization; be placed on growing the grain 36h in 4 ℃ of environment; filtering crystallisate, cryodrying get laurotetanine 25g, content 98.9%.
Embodiment 6:
Get 80 order Root of Mountain Spicy Tree 30kg and place extraction kettle, sealing will be extracted temperature and be transferred to 45 ℃, and the knockout tower temperature transfers to 55 ℃, extract pressure 34.7Mpa, and parsing pressure is 13.2Mpa, CO 2Gas is emitted from steel cylinder, through behind the gas purifier in liquefied pot, liquefaction, enter storage tank with high-pressure metering pump with CO 2Send into cleaner, to assigned temperature and pressure, flow velocity 29kg/h opens relief valve by preheater, by relief valve control above-mentioned parameter, dynamic extraction 3 hours.Emit extract after the shutdown; collect extract 2.8kg; add D152 macropore weakly acidic cation-exchange resin post; 3% ammoniacal liquor wash-out; collecting down, the fluid injection concentrating under reduced pressure becomes medicinal extract; add the chloroform dissolving, filtrate pumps into alumina column, earlier with 4BV methanol solution wash-out impurity; use methylene chloride-methanol (1: 1), methylene chloride-methanol (1: 9) wash-out again; high Liquid Detection is collected the high density flow point, reclaims reagent to beginning crystallization; be placed on growing the grain 48h in 7 ℃ of environment; filtering crystallisate, cryodrying get laurotetanine 32g, content 99.3%.
Embodiment 7:
Get 80 order Root of Mountain Spicy Tree 20kg and place extraction kettle, sealing will be extracted temperature and be transferred to 41 ℃, and the knockout tower temperature transfers to 53 ℃, extract pressure 33.3Mpa, and parsing pressure is 8.6Mpa, CO 2Gas is emitted from steel cylinder, through behind the gas purifier in liquefied pot, liquefaction, enter storage tank with high-pressure metering pump with CO 2Send into cleaner, to assigned temperature and pressure, flow velocity 31kg/h opens relief valve by preheater, by relief valve control above-mentioned parameter, dynamic extraction 2 hours.Emit extract after the shutdown; collect extract 1.6kg; add 001 * Final 8 acidic cation-exchange resin post; 4% ammoniacal liquor wash-out; collecting down, the fluid injection concentrating under reduced pressure becomes medicinal extract; add the chloroform dissolving, filtrate pumps into alumina column, earlier with 3BV methanol solution wash-out impurity; use methylene chloride-methanol (1: 1), methylene chloride-methanol (1: 9) wash-out again; high Liquid Detection is collected the high density flow point, reclaims reagent to beginning crystallization; be placed on growing the grain 30h in 10 ℃ of environment; filtering crystallisate, cryodrying get laurotetanine 23g, content 99.1%.

Claims (5)

1. the extracting method of a laurotetanine is characterized in that comprising following steps:
A. supercritical CO 2Extraction: will be rich in the pulverizing medicinal materials 40-80 order of laurotetanine, drop in the extraction kettle, and after the warming apparatus works better, open compression pump and be pressurized to 22.5-36.8MPa, extraction temperature 30-60 ℃, pumping liquid CO 2And entrainment agent, keeping above-mentioned pressure and temperature 0.5-3 hour, separating still is at pressure 6.8-14.7MPa, and extract is collected in temperature 40-60 ℃ of decompression parsing separation down;
B. ion-exchange: the said extracted thing is added Zeo-karb, 2-8% ammoniacal liquor wash-out, following fluid injection concentrate drying;
C. column chromatography purification: above-mentioned dry thing is dissolved with minimum of chloroform, add alumina chromatographic column, methylene chloride-methanol mixed solvent wash-out, collect laurotetanine high-content wash-out part, reclaim reagent, under cold condition, leave standstill growing the grain to beginning crystallization, filter, be drying to obtain product.
2. the extracting method of laurotetanine according to claim 1 is characterized in that the described CO of step a. 2Flow control is 26-33kg/h, and entrainment agent is ethanol or methyl alcohol, consumption 2-5%.
3. the extracting method of laurotetanine according to claim 1 is characterized in that the described Zeo-karb of step b. is strongly acidic styrene type cation exchange resin 001 * 8, macropore weak acid acrylic acid type cation exchange resin D152, weakly acidic cationic exchanger resin 724 or 732.
4. the extracting method of laurotetanine according to claim 1, it is characterized in that the described aluminum oxide of step c is a 100-200 purpose alkali alumina, gradient elution is 2-4BV methyl alcohol → 4-6BV methylene chloride-methanol (1: 1) mixing solutions → 3-8BV methylene chloride-methanol (1: 9) mixing solutions.
5. the extracting method of laurotetanine according to claim 1, it is characterized in that the described growing the grain condition of step c: temperature 4-10 ℃, rearing crystal time is 16-48h.
CN201010293245XA 2010-09-27 2010-09-27 Extracting method of laurotetanine Pending CN102040557A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432534A (en) * 2011-12-11 2012-05-02 卞毓平 Method for extracting norisoboldine from combined spicebush roots
CN103194311A (en) * 2013-04-22 2013-07-10 湖南康瑞琦生物科技有限公司 Process method for extracting litsea cubeba oil by using supercritical CO2

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432534A (en) * 2011-12-11 2012-05-02 卞毓平 Method for extracting norisoboldine from combined spicebush roots
CN103194311A (en) * 2013-04-22 2013-07-10 湖南康瑞琦生物科技有限公司 Process method for extracting litsea cubeba oil by using supercritical CO2

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Application publication date: 20110504