CN102250092B - Preparation process of alkaloid tabersonine - Google Patents
Preparation process of alkaloid tabersonine Download PDFInfo
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- CN102250092B CN102250092B CN 201110237688 CN201110237688A CN102250092B CN 102250092 B CN102250092 B CN 102250092B CN 201110237688 CN201110237688 CN 201110237688 CN 201110237688 A CN201110237688 A CN 201110237688A CN 102250092 B CN102250092 B CN 102250092B
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Abstract
The invention relates to a preparation process of alkaloid tabersonine, relating to the technical field of biopharmaceuticals. The traditional biological preparation process of the tabersonine has the problems of large solvent loss amount, high cost, large water consumption, high adsorbent resin price, and the like. The preparation process of the alkaloid tabersonine, disclosed by the invention, comprises the following steps of: squeezing voacanga seeds; carrying out solvent extraction; carrying out acid water extraction and washing; and carrying out acid water purification, alkalinization and extraction. According to the preparation process disclosed by the invention, solvent dimethylbenzene which has high boiling point, low cost and easiness in obtaining is adopted as an extractant, and a mode of the acid water extraction and washing is adopted, and therefore, the using amount and the treatment capacity of acid water are reduced; extracted diluted acid water is treated by adopting the dimethylbenzene, and therefore the adsorption washing or repeated salt transformation purification process of the conventional macroporous resin is saved; the content of the tabersonine reaches more than 98 percent, and the extraction ratio is between 1.8 percent and 2.0 percent; in addition, according to the invention, production cost is reduced, and water consumption and solvent consumption are reduced.
Description
Technical field
The present invention relates to biological pharmacy technical field, specifically a kind of preparation technology of alkaloid tabersonine.
Background technology
Tabersonine, English name Tabersonine, CAS NO 4429-63-4, its chemical name is Aspidospermidine-3-carboxylic acid, 2,3,6,7-tetradehydro-(5 α, 12 β, 19 γ)-methyl seter, molecular formula is C
21h
24n
2o
2,molecular weight is 336.42.Be generally oily liquids, purity is higher is the white powder solid, and its hydrochloride is C
21h
24n
2o
2hCl, fusing point is 196 ℃, [α]
d 25-318
.(C=0.58, ethanol), IR: λ cm
-1: 3365,1690,1630,1615; UV λ max (Loge): 228 (4.03), 298 (4.02), 331 (4.16).
Tabersonine is a kind of good medicinal material, and step-down, antitumor, hypoglycemic and diuretic properties and the depression caused for apoplexy sequela, ischemia hypertensive encephalopathy and cerebro-vascular diseases, anxious and emotional lability are arranged.Be applicable to the symptom that the early ageing brain degenerates and eliminate, as dizzy, headache is losing one's memory etc., is also the important source material of synthetic cancer therapy drug vincamine and vinpocetin simultaneously.
Tabersonine has two kinds of preparation technologies at present, and a kind of is complete synthesizing process; Another kind is the biological extraction method, is mainly to extract from the seed of African Voacanga.
For the biological extraction method, there is following problem in the disclosed technical scheme of patent US3758478, US3892755 and CN101250188A:
1. in extracting, use a large amount of lower boilings, volatile solvent, as: one or more in methylene dichloride, chloroform, sherwood oil, methyl alcohol or ethanol equal solvent, through repeatedly extracting, separate and evaporating, large production practice prove, extract qualified tabersonine, the solvent loss amount has all surpassed 25%, and the industrialization cost is high.
2. all use a large amount of diluted acid water (all below 2%) extracting and washing product, need the wastewater flow rate of processing large, do not mention water saving measures.
3. for purified product, some patents are used repeatedly crystallization process, and extraction yield is low; The macroporous adsorbent resin of using had is purified, and the one, need with a large amount of eluting solvents, need recycle and reuse; The 2nd, repeatedly the activation treatment regenerating resin, need use a large amount of diluted acids, diluted alkaline and alcohols equal solvent; The 3rd, macroporous adsorbent resin is expensive, and price is 200 yuan/Kg at present; The 4th, amount of resin used is large, extracts 1 kilogram of Voacanga seed (the alkaloid tabersonine that approximately contains 20 grams), need the macroporous adsorbent resin of 10 kilograms, otherwise the tabersonine content extracted does not reach more than 98%.
Summary of the invention
The preparation technology who the purpose of this invention is to provide a kind of alkaloid tabersonine is large with the extraction solvent-oil ratio that solves prior art, wastewater treatment capacity is large; Purify and resin column purifies and separates difficulty and high expensive, be unfavorable for the problem of industrialized production.
Technical scheme of the present invention mainly comprises the following steps:
One, the processing of Voacanga seed: with grease press, seed is crushed, collect oil phase, squeeze cake is ground into 80 orders-100 order through pulverizer again, stand-by;
Two, solvent extraction: dimethylbenzene and crushed material quality are than being 2-5: 1, be heated to 35 ℃-55 ℃ of temperature, and stir 3 hours, be cooled to 20 ℃, suction filtration is to dry, decompression and solvent recovery, residual oil phase is collected oil phase with squeezing and is merged, stand-by;
Three, sour water extracting and washing: step 1 and two merging oil phase is divided into to two parts, and a copy of it be take dimethylbenzene and oil phase mass ratio after the 5-10:1 dilution, stirs 30 minutes; The aqueous sulfuric acid that is 2.5%-3.5% with mass percent concentration divides extracting and washing 2-3 time; During each extracting and washing, stir 1 hour, static 2 hours, layering, isolated organic phase and sour water phase; The sour water of extracting and washing is I mutually for the first time, and the sour water of extracting and washing is II mutually for the second time, and the sour water of extracting and washing is III mutually for the third time; A oil phase same method extracting and washing in addition, for aqueous sulfuric acid, sour water II, sour water III substitute, and acid rinsing sour water II for the first time, for the second time by new aqueous sulfuric acid or acid rinsing sour water II for the first time, use for the second time the sour water III, use for the third time new aqueous sulfuric acid; Merge the washing sour water, stand-by;
Four, sour water purifying: by the sour water merged in step 3, add discoloring agent, the agent of oiliness impurity absorption, control pH=2-3, stir 2-5h, filter, sour water is stand-by;
Five, alkalization, extraction: the sour water after purifying, the ammoniacal liquor that is 20% with mass percent concentration is adjusted pH=8.5-10, use again the recovery dimethylbenzene of the 10%-15% of sour water weight, extract 2-3 time, after merging extracting and demixing, isolated dimethylbenzene, the siccative Sodium sulfate anhydrous.min(99) that adds again dimethylbenzene quality 5%-7%, stir dry 2 hours, filters, the evaporated under reduced pressure solvent, obtain the alkaloid tabersonine.
Advantage of the present invention is:
1), adopt the extracting mode that squeezing is pulverized and solvent extraction combines, will extract quantity of solvent and greatly reduce, 1 ton of Voacanga seed of existing technique extraction, approximately need to have enough to meet the need 10 tons of solvents, the present invention only needs the 3-4 ton.
2) adopt high boiling point, not volatile, and the relatively inexpensive solvent xylene be easy to get, in the industrialization such as centrifugation, underpressure distillation operation, greatly reduced the loss amount of solvent.Existing technological test proves, with sherwood oil or methylene dichloride or one or more mixed solvents such as methyl alcohol or normal hexane, the solvent loss rate is all over 30%, and solvent loss rate of the present invention is at 5%-10%.
3) in the sour water extracting and washing, reduced wastewater flow rate, the industrialization data, extract 1 ton of Voacanga, reduces 1 ton of wastewater flow rate.
4) during purifying products, without the macroporous resin adsorption washing or repeatedly turn the salt purge process, by selecting sorbent material unslaked lime or magnesium oxide, process the diluted acid water of extraction, content has reached more than 98%, and extraction yield is at 1.8%-2.05%.
The accompanying drawing explanation
Fig. 1 is the process flow sheet of prior art;
Fig. 2 is process flow sheet of the present invention.
Embodiment 1
One, the pre-treatment of Voacanga seed: the Voacanga seed 50Kg by ripe, do not need drying, directly use the grease press cold press, collect oil phase weight 10Kg, squeeze cake 38Kg, be ground into 80 orders with pulverizer, stand-by.
Two, solvent extraction: by the dimethylbenzene of 190Kg (content >=98%, boiling point are for 138.35 ℃-144.42 ℃), join in the cake slag after 38Kg pulverizes, under 35 ℃, stir 3 hours, be cooled to 20 ℃, suction filtration is to dry, the evaporated under reduced pressure solvent obtains oily 3Kg, stand-by.
Three, sour water extracting and washing: by oily 6.5Kg, add dimethylbenzene 65Kg, stir 30 minutes; Extracting and washing for the first time: adding mass percent concentration is 2.5% aqueous sulfuric acid 50Kg, stirs 1 hour, and static 2 hours, layering, isolated organic phase and sour water phase, and sour water is I mutually.
Extracting and washing for the second time: add the aqueous sulfuric acid 50Kg that mass percent concentration is 3.5% in organic phase again, stir 1 hour, static 2 hours, layering, isolated organic phase and sour water phase, and sour water is II mutually, stand-by; Sour water after mercury potassium iodide solution qualitative detection with 4.5% extracts for the second time, if without white precipitate, illustrate and there is no alkaloid; After the extraction secondary, the basic extraction fully.
Get oily 6.5Kg again, operate the samely, difference is that acid rinsing sour water II, use new aqueous sulfuric acid for the second time for the first time.
Four, sour water purifying: the sour water 150Kg by the merging in step 3, add powdered carbon 0.75Kg, unslaked lime 0.75Kg, stir 3 hours, filters, and sour water is stand-by.
Five, alkalization, extraction: the sour water after the 150Kg purifying, add the ammoniacal liquor that mass percent concentration is 20%, adjust pH=9.5; With the xylene extraction secondary reclaimed, the amount that at every turn adds dimethylbenzene is 15Kg, stir 30 minutes at every turn, and after static 1 hour, layering, separating dimethyl benzene; Merge extraction fluid, layering, the dimethylbenzene after separation, then add the Sodium sulfate anhydrous.min(99) of 7.5Kg, and stir dry 2 hours, filter, the evaporated under reduced pressure solvent, obtain the alkaloid tabersonine 0.95Kg that content is greater than 98%.The Voacanga of relative 50Kg, extraction yield is 1.9%.
Embodiment 2
One, the pre-treatment of Voacanga seed: the Voacanga seed 100Kg by ripe, do not need drying, directly use the grease press cold press, collect oil phase weight 25Kg, squeeze cake 70Kg, be ground into 100 orders with pulverizer, stand-by.
Two, solvent extraction: 140Kg dimethylbenzene (content >=98%, boiling point are for 138.35 ℃-144.42 ℃) is added in the cake slag after 70Kg pulverizes, under 55 ℃, stir 3 hours, cool to 20 ℃, suction filtration is to dry, and the evaporated under reduced pressure solvent obtains oily 5Kg.
Three, sour water extracting and washing: by oily 15Kg, add dimethylbenzene 75Kg, stir 30 minutes;
Extracting and washing for the first time: add 3.5% aqueous sulfuric acid 50Kg, stir 1 hour, static 2 hours, layering, sour water is I mutually.
Extracting and washing for the second time: organic phase adds 3.5% aqueous sulfuric acid 50Kg again, stirs 1 hour, and static 2 hours, layering, sour water is II mutually.
Extracting and washing for the third time: organic phase adds 3.5% aqueous sulfuric acid 50Kg again, stirs 1 hour, and static 2 hours, layering, sour water is III mutually; Sour water after mercury potassium iodide solution qualitative detection the 3rd extraction with 4.5%, if without white precipitate, illustrate and there is no alkaloid; After extracting three times, the basic extraction fully.
Get oily 6.5Kg again, operate the samely, difference is that acid rinsing sour water II, use the sour water III for the second time for the first time, uses for the third time new aqueous sulfuric acid.
Four, sour water purifying: the sour water 200Kg by merging in step 3, add powdered carbon 4Kg, magnesium oxide 4Kg, stir 2 hours, filters, and sour water is stand-by.
Five, alkalization, extraction: the sour water after the 200Kg purifying, use 20% ammoniacal liquor, adjust pH=9.5, by the xylene extraction of recovery three times, add the dimethylbenzene amount is 30Kg at every turn, stir 30 minutes at every turn, after static 1 hour, layering, separating dimethyl benzene; Merge the dimethylbenzene after extracting and demixing, then add the Sodium sulfate anhydrous.min(99) of 14Kg, stir dry 2 hours, filter, the evaporated under reduced pressure solvent, obtain the alkaloid tabersonine 2.05Kg that content is greater than 98%.The Voacanga of relative 100Kg, extraction yield is 2.0%.
Embodiment 3
One, the pre-treatment of Voacanga seed: the Voacanga seed 100Kg by ripe, do not need drying, directly use the grease press cold press, collect oil phase weight 25Kg, squeeze cake 70Kg, be ground into 90 orders with pulverizer, stand-by.
Two, solvent extraction: 175Kg dimethylbenzene (content >=98%, boiling point are for 138.35 ℃-144.42 ℃) is added in the cake slag after 70Kg pulverizes, under 45 ℃, stir 3 hours, cool to 20 ℃, suction filtration is to dry, and the evaporated under reduced pressure solvent obtains oily 5Kg.
Three, sour water extracting and washing: by oily 15Kg, add dimethylbenzene 105Kg, stir 30 minutes;
Extracting and washing for the first time: add 3.0% aqueous sulfuric acid 50Kg, stir 1 hour, static 2 hours, layering, sour water is I mutually.
Extracting and washing for the second time: organic phase adds 3.0% aqueous sulfuric acid 50Kg again, stirs 1 hour, and static 2 hours, layering, sour water is II mutually.
Extracting and washing for the third time: organic phase adds 3.0% aqueous sulfuric acid 50Kg again, stirs 1 hour, and static 2 hours, layering, sour water is III mutually; Sour water after mercury potassium iodide solution qualitative detection the 3rd extraction with 4.5%, if without white precipitate, illustrate and there is no alkaloid; After extracting three times, the basic extraction fully.
Get oily 6.5Kg again, operate the samely, difference is that acid rinsing sour water II, use the sour water III for the second time for the first time, uses for the third time new aqueous sulfuric acid.
Four, sour water purifying: the sour water 200Kg by merging in step 3, add powdered carbon 3Kg, magnesium oxide 3.0Kg, stir 2 hours, filters, and sour water is stand-by.
Five, alkalization, extraction: the sour water after the 200Kg purifying, use 20% ammoniacal liquor, adjust pH=9.5, by the xylene extraction of recovery three times, add the dimethylbenzene amount is 25Kg at every turn, stir 30 minutes at every turn, after static 1 hour, layering, separating dimethyl benzene; Merge the dimethylbenzene after extracting and demixing, then add the Sodium sulfate anhydrous.min(99) of 12Kg, stir dry 2 hours, filter, the evaporated under reduced pressure solvent, obtain the alkaloid tabersonine 2.05Kg that content is greater than 98%.The Voacanga of relative 100Kg, extraction yield is 2.05%.
Obviously, the above embodiment of the present invention is only for example of the present invention clearly is described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give all embodiments exhaustive.Every still row in protection scope of the present invention of apparent variation that technical scheme of the present invention extends out or change that belong to.
Claims (5)
1. the preparation technology of an alkaloid tabersonine is characterized in that comprising following processing step:
One, the processing of Voacanga seed: with grease press, seed is crushed, collect oil phase, squeeze cake is ground into 80 orders-100 order through pulverizer again, stand-by;
Two, solvent extraction: dimethylbenzene and crushed material quality are than being 2-5: 1, be heated to 35 ℃-55 ℃ of temperature, and stir 3 hours, be cooled to 20 ℃, suction filtration is to dry, decompression and solvent recovery, residual oil phase is collected oil phase with squeezing and is merged, stand-by;
Three, sour water extracting and washing: step 1 and two merging oil phase is divided into to two parts, and a copy of it be take dimethylbenzene and oil phase mass ratio after the 5-10:1 dilution, stirs 30 minutes; The aqueous sulfuric acid that is 2.5%-3.5% with mass percent concentration divides extracting and washing 2-3 time; During each extracting and washing, stir 1 hour, static 2 hours, layering, isolated organic phase and sour water phase; The sour water of extracting and washing is I mutually for the first time, and the sour water of extracting and washing is II mutually for the second time, and the sour water of extracting and washing is III mutually for the third time; A oil phase same method extracting and washing in addition, for aqueous sulfuric acid, sour water II, sour water III substitute, and acid rinsing sour water II for the first time, for the second time by new aqueous sulfuric acid or acid rinsing sour water II for the first time, use for the second time the sour water III, use for the third time new aqueous sulfuric acid; Merge the washing sour water, stand-by;
Four, sour water purifying: by the sour water merged in step 3, add discoloring agent, the agent of oiliness impurity absorption, control pH=2-3, stir 2-5h, filter, sour water is stand-by;
Five, alkalization, extraction: the sour water after purifying, the ammoniacal liquor that is 20% with mass percent concentration is adjusted pH=8.5-10, use again the recovery dimethylbenzene of the 10%-15% of sour water weight, extract 2-3 time, after merging extracting and demixing, isolated dimethylbenzene, the siccative Sodium sulfate anhydrous.min(99) that adds again dimethylbenzene quality 5%-7%, stir dry 2 hours, filters, the evaporated under reduced pressure solvent, obtain the alkaloid tabersonine.
2. the preparation technology of a kind of alkaloid tabersonine as claimed in claim 1, is characterized in that the discoloring agent described in step 4 refers to powdered carbon, the 0.5%-2.0% that add-on is sour water weight; The agent of oiliness impurity absorption refers to unslaked lime or magnesium oxide, the 0.5%-2.0% that add-on is sour water weight.
3. the preparation technology of a kind of alkaloid tabersonine as claimed in claim 1, is characterized in that the discoloring agent described in step 4 refers to powdered carbon, and add-on is 1.5% of sour water weight; The agent of oiliness impurity absorption refers to unslaked lime or magnesium oxide, and add-on is 1.5% of sour water weight.
4. the preparation technology of a kind of alkaloid tabersonine as claimed in claim 1, is characterized in that the xylene extraction with recovery described in step 5 2-3 time, refers to each stirring 30 minutes, static 1 hour.
5. the preparation technology of a kind of alkaloid tabersonine as claimed in claim 1, is characterized in that the aqueous sulfuric acid mass percent concentration described in step 3 is preferably 3.0%.
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| CN102746303A (en) * | 2012-06-21 | 2012-10-24 | 永州市鑫盈建材有限公司 | Method for extracting effective component of Voacanga seed |
| CN108853043B (en) * | 2018-09-28 | 2020-11-13 | 郑士平 | Medicine for treating central diabetes insipidus and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3758478A (en) * | 1971-07-16 | 1973-09-11 | J Poisson | Process of obtaining tabersonine |
| CN101250188A (en) * | 2008-03-25 | 2008-08-27 | 西安皓天生物工程技术有限责任公司 | Technique for preparing willow leaf tabersonine |
| CN102050822A (en) * | 2010-12-28 | 2011-05-11 | 陕西嘉禾植物化工有限责任公司 | Method for extracting tabersonine from voacanga seed |
| CN102060856A (en) * | 2010-12-21 | 2011-05-18 | 英杰华纳（厦门）生物工程有限公司 | Method for extracting tabersonine from voacanga seeds |
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2011
- 2011-08-18 CN CN 201110237688 patent/CN102250092B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3758478A (en) * | 1971-07-16 | 1973-09-11 | J Poisson | Process of obtaining tabersonine |
| CN101250188A (en) * | 2008-03-25 | 2008-08-27 | 西安皓天生物工程技术有限责任公司 | Technique for preparing willow leaf tabersonine |
| CN102060856A (en) * | 2010-12-21 | 2011-05-18 | 英杰华纳（厦门）生物工程有限公司 | Method for extracting tabersonine from voacanga seeds |
| CN102050822A (en) * | 2010-12-28 | 2011-05-11 | 陕西嘉禾植物化工有限责任公司 | Method for extracting tabersonine from voacanga seed |
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