CN102558271A - Industrial preparation method of pseudoginsenoside - Google Patents
Industrial preparation method of pseudoginsenoside Download PDFInfo
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- CN102558271A CN102558271A CN2012100121609A CN201210012160A CN102558271A CN 102558271 A CN102558271 A CN 102558271A CN 2012100121609 A CN2012100121609 A CN 2012100121609A CN 201210012160 A CN201210012160 A CN 201210012160A CN 102558271 A CN102558271 A CN 102558271A
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Abstract
The invention relates to a novel industrial preparation of pseudoginsenoside. Macroporous adsorbent resin, a solvent extraction method, silica gel vacuum column chromatography and an oxidative alkaline hydrolysis method are adopted in the method, the preparation process is simplified, the product yield is increased by more than 1 percent, the product purity is increased by more than 90 percent, and the method is suitable for industrial production.
Description
Technical field:
The present invention relates to a kind of novel method of industrial preparation Ocotillol, this method has adopted alkali oxide solution and recrystallization, has simplified preparation technology, has improved product yield (more than 1%) and purity (more than 90%), is fit to suitability for industrialized production.Belong to the improvement of traditional Chinese medicine extraction separating technology and technology for hydrolyzing.
Background technology:
The structural formula of pseudo-ginsenoside F 11 and aglycon thereof is following:
Ginsenoside has a wide range of applications at field of medicaments, and has been developed to many valuable drug.Current research shows that pseudo-ginsenoside F 11 has the good disordered brain function that improves, and improves learning and memory ability and anti-senile dementia effect, the very potential kind new medicine that is developed to of the verivate of its aglycon.
Pseudo-ginsenoside F 11 extensively is present in the plant of Panax, and particularly content is the highest in Radix Panacis Quinquefolii, and stem and leaf of Radix Panacis Quinquefolii is the position of the pseudo-ginsenoside F 11 that contains maximum up to the present found in the panax species.Can prepare Ocotillol by pseudo-ginsenoside F 11.
The former preparation method of Ocotillol has methods such as acidolysis, enzymolysis, alkaline hydrolysis.Acid hydrolyzation can cause that the aglycon structure changes, and can not get former aglycon enzymolysis process more complicated, productive rate is low, cost is higher, the Smith edman degradation Edman more complicated that operates; The alkaline hydrolysis method utilizes alkaline condition to make ginsenoside be able to degrade fully; Reaction temperature with, but need HTHP, conversion unit is had requirement; And preparative-scale is little, can not well realize suitability for industrialized production.The alkali oxide solution develops into the logical oxygen of normal pressure etc. by conditions such as original pressurization, high temperature and improves one's methods.
Summary of the invention:
Can keep aglycon structure and constant secondary aglycon and the aglycon of steric configuration for the alkaline hydrolysis method is prepared, constantly improve the reaction conditions of alkaline hydrolysis method, solve the defective that original preparing method's pressurization, high temperature etc. are not suitable for suitability for industrialized production; Present method is introduced the method for alkali oxide solution and recrystallization; Carry out the preparation of Ocotillol, reduced cost, improved productive rate; Simplify operation steps, be suitable for suitability for industrialized production.
The present invention can implement through the following step:
A. get in the propyl carbinol that a pseudo-ginsenoside F 11 is dissolved in dehydration, add 5 ~ 15 times of amount propyl carbinol sodium.Under the condition of logical oxygen, be heated to 80 ~ 100 ℃, react and stopped in about 6 ~ 12 hours.Reaction solution is cooled to room temperature,, discards water layer, the n-butanol layer reclaim under reduced pressure with the saturated washing of propyl carbinol three times;
B. the reaction product of gained is used dissolved in distilled water, the aqueous solution discards water layer with ethyl acetate extraction three times.Organic layer dehydrates with anhydrous magnesium sulfate, concentrates to obtain oxidation alkaline hydrolysis crude product;
C. crude product is dissolved with a small amount of methylene dichloride, filter.Add absolute ethyl alcohol and carry out recrystallization, place post crystallization and separate out.Can obtain the pure article of Ocotillol repeatedly several times.Product is colourless needle (dichloromethane-ethanol), mp211-213 ℃ (MeOH), and 10% ethanol solution of sulfuric acid shows purple, Liebermann-Burchard reacting positive.
1H-NMR(300MHz,?C
5D
5N)：0.91(3H,?s,?H-30),?0.96(3H,?s,?H-18),?1.10(3H,?s,?H-19),?1.24(3H,?s,?H-26),?1.25(3H,?s,?H-21),?1.42(3H,?s,?H-28),?1.46(3H,?s,?H-27),?1.97(3H,?s,?H-29),?3.49(1H,?dd,?
J=5.4,?11.1Hz,?H-3),?3.69(1H,?dt,?
J=4.5,?10.4Hz,?H-12),?3.92(1H,?dd,?
J=6.9,?8.3Hz,?H-24),?4.39(1H,?m,?H-6)。
13C-NMR(75MHz,?C
5D
5N)：39.4(C-l),?28.1(C-2),?78.4(C-3),?40.4(C-4),?61.9(C-5),?67.7(C-6),?47.5(C-7),?41.4(C-8),?50.5(C-9),?39.3(C-10),?32.4(C-11),?71.2(C-12),?48.4(C-13),?52.1(C-14),?31.7(C-15),?25.5(C-16),?49.4(C-17),?17.8(C-18),?17.2(C-19),?86.7(C-20),?27.0(C-21),?32.8(C-22),?28.8(C-23),?85.6(C-24),?70.3(C-25),?27.2(C-26),?27.6(C-27),?31.9(C-28),?16.5(C-29),?18.3(C-30)。
Optimum condition of the present invention:
The a step.: the pseudo-ginsenoside F 11 solvent temperature is preferably 90-95 ℃, and the propyl carbinol add-on is preferably 8-12 and doubly measures, and the reaction times is preferably 8-10 hour.
Present method has reduced cost, has simplified operation steps, and the later stage, product purity can reach more than 90% through recrystallization, and yield can reach more than 1%.The present invention simultaneously utilizes pseudo-ginsenoside F 11 as raw material first, adopts direct oxidation alkaline hydrolysis method to obtain Ocotillol, has optimized the hydrolysis reaction condition, and method is simple to operate, and product purity is higher, is adapted to industrial production requirement.
Embodiment:
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment 1:The preparation of Ocotillol:
100g PF11 is dissolved in the propyl carbinol of dehydration, adds 500ml propyl carbinol sodium.Under the condition of logical oxygen, be heated to 80 ℃, react and stopped in 6 hours.Reaction solution is cooled to room temperature,, discards water layer, the n-butanol layer reclaim under reduced pressure with the saturated washing of propyl carbinol three times.The reaction product of gained is used dissolved in distilled water, and the aqueous solution discards water layer with ethyl acetate extraction three times.Organic layer dehydrates with anhydrous magnesium sulfate, concentrates to obtain oxidation alkaline hydrolysis crude product.Crude product is dissolved with a small amount of methylene dichloride, filter.Add absolute ethyl alcohol and carry out recrystallization, place post crystallization and separate out.Can obtain Ocotillol 61g several times repeatedly, sapogenin content is 95% (HPLC detection), and alkali oxide solution productive rate is 61.0%.Product is colourless needle (dichloromethane-ethanol), mp211-213 ℃ (MeOH), and 10% ethanol solution of sulfuric acid shows purple, Liebermann-Burchard reacting positive.
1H-NMR(300MHz,?C
5D
5N)：0.91(3H,?s,?H-30),?0.96(3H,?s,?H-18),?1.10(3H,?s,?H-19),?1.24(3H,?s,?H-26),?1.25(3H,?s,?H-21),?1.42(3H,?s,?H-28),?1.46(3H,?s,?H-27),?1.97(3H,?s,?H-29),?3.49(1H,?dd,?
J=5.4,?11.1Hz,?H-3),?3.69(1H,?dt,?
J=4.5,?10.4Hz,?H-12),?3.92(1H,?dd,?
J=6.9,?8.3Hz,?H-24),?4.39(1H,?m,?H-6)。
13C-NMR(75MHz,?C
5D
5N)：39.4(C-l),?28.1(C-2),?78.4(C-3),?40.4(C-4),?61.9(C-5),?67.7(C-6),?47.5(C-7),?41.4(C-8),?50.5(C-9),?39.3(C-10),?32.4(C-11),?71.2(C-12),?48.4(C-13),?52.1(C-14),?31.7(C-15),?25.5(C-16),?49.4(C-17),?17.8(C-18),?17.2(C-19),?86.7(C-20),?27.0(C-21),?32.8(C-22),?28.8(C-23),?85.6(C-24),?70.3(C-25),?27.2(C-26),?27.6(C-27),?31.9(C-28),?16.5(C-29),?18.3(C-30)。
Embodiment 2:The preparation of Ocotillol:
The 100g pseudo-ginsenoside F 11 is dissolved in the propyl carbinol of dehydration, adds 1500ml propyl carbinol sodium.Under the condition of logical oxygen, be heated to 100 ℃, react and stopped in 12 hours.Reaction solution is cooled to room temperature,, discards water layer, the n-butanol layer reclaim under reduced pressure with the saturated washing of propyl carbinol three times.The reaction product of gained is used dissolved in distilled water, and the aqueous solution discards water layer with ethyl acetate extraction three times.Organic layer dehydrates with anhydrous magnesium sulfate, concentrates to obtain oxidation alkaline hydrolysis crude product.Crude product is dissolved with a small amount of methylene dichloride, filter.Add absolute ethyl alcohol and carry out recrystallization, place post crystallization and separate out.Can obtain Ocotillol 60g several times repeatedly, sapogenin content is 96% (HPLC detection), and alkali oxide solution productive rate is 60.0%.Product is colourless needle (dichloromethane-ethanol), mp211-213 ℃ (MeOH), and 10% ethanol solution of sulfuric acid shows purple, Liebermann-Burchard reacting positive.
1H-NMR(300MHz,?C
5D
5N)：0.91(3H,?s,?H-30),?0.96(3H,?s,?H-18),?1.10(3H,?s,?H-19),?1.24(3H,?s,?H-26),?1.25(3H,?s,?H-21),?1.42(3H,?s,?H-28),?1.46(3H,?s,?H-27),?1.97(3H,?s,?H-29),?3.49(1H,?dd,?
J=5.4,?11.1Hz,?H-3),?3.69(1H,?dt,?
J=4.5,?10.4Hz,?H-12),?3.92(1H,?dd,?
J=6.9,?8.3Hz,?H-24),?4.39(1H,?m,?H-6)。
13C-NMR(75MHz,?C
5D
5N)：39.4(C-l),?28.1(C-2),?78.4(C-3),?40.4(C-4),?61.9(C-5),?67.7(C-6),?47.5(C-7),?41.4(C-8),?50.5(C-9),?39.3(C-10),?32.4(C-11),?71.2(C-12),?48.4(C-13),?52.1(C-14),?31.7(C-15),?25.5(C-16),?49.4(C-17),?17.8(C-18),?17.2(C-19),?86.7(C-20),?27.0(C-21),?32.8(C-22),?28.8(C-23),?85.6(C-24),?70.3(C-25),?27.2(C-26),?27.6(C-27),?31.9(C-28),?16.5(C-29),?18.3(C-30)。
Embodiment 3:The preparation of Ocotillol:
The 100g pseudo-ginsenoside F 11 is dissolved in the propyl carbinol of dehydration, adds 1000ml propyl carbinol sodium.Under the condition of logical oxygen, be heated to 95 ℃, react and stopped in 10 hours.Reaction solution is cooled to room temperature,, discards water layer, the n-butanol layer reclaim under reduced pressure with the saturated washing of propyl carbinol three times.The reaction product of gained is used dissolved in distilled water, and the aqueous solution discards water layer with ethyl acetate extraction three times.Organic layer dehydrates with anhydrous magnesium sulfate, concentrates to obtain oxidation alkaline hydrolysis crude product.Crude product is dissolved with a small amount of methylene dichloride, filter.Add absolute ethyl alcohol and carry out recrystallization, place post crystallization and separate out.Can obtain Ocotillol 63g several times repeatedly, sapogenin content is 95% (HPLC detection), and alkali oxide solution productive rate is 63.0%.Product is colourless needle (dichloromethane-ethanol), mp211-213 ℃ (MeOH), and 10% ethanol solution of sulfuric acid shows purple, Liebermann-Burchard reacting positive.
1H-NMR(300MHz,?C
5D
5N)：0.91(3H,?s,?H-30),?0.96(3H,?s,?H-18),?1.10(3H,?s,?H-19),?1.24(3H,?s,?H-26),?1.25(3H,?s,?H-21),?1.42(3H,?s,?H-28),?1.46(3H,?s,?H-27),?1.97(3H,?s,?H-29),?3.49(1H,?dd,?
J=5.4,?11.1Hz,?H-3),?3.69(1H,?dt,?
J=4.5,?10.4Hz,?H-12),?3.92(1H,?dd,?
J=6.9,?8.3Hz,?H-24),?4.39(1H,?m,?H-6)。
13C-NMR(75MHz,?C
5D
5N)：39.4(C-l),?28.1(C-2),?78.4(C-3),?40.4(C-4),?61.9(C-5),?67.7(C-6),?47.5(C-7),?41.4(C-8),?50.5(C-9),?39.3(C-10),?32.4(C-11),?71.2(C-12),?48.4(C-13),?52.1(C-14),?31.7(C-15),?25.5(C-16),?49.4(C-17),?17.8(C-18),?17.2(C-19),?86.7(C-20),?27.0(C-21),?32.8(C-22),?28.8(C-23),?85.6(C-24),?70.3(C-25),?27.2(C-26),?27.6(C-27),?31.9(C-28),?16.5(C-29),?18.3(C-30)。
Embodiment 4:The preparation of Ocotillol:
F11 is dissolved in the propyl carbinol of dehydration with the anthropomorphic ginseng of 1000g soap, adds 8000ml propyl carbinol sodium.Under the condition of logical oxygen, be heated to 85 ℃, react and stopped in 8 hours.Reaction solution is cooled to room temperature,, discards water layer, the n-butanol layer reclaim under reduced pressure with the saturated washing of propyl carbinol three times.The reaction product of gained is used dissolved in distilled water, and the aqueous solution discards water layer with ethyl acetate extraction three times.Organic layer dehydrates with anhydrous magnesium sulfate, concentrates to obtain oxidation alkaline hydrolysis crude product.Crude product is dissolved with methylene dichloride, filter.Add absolute ethyl alcohol and carry out recrystallization, place post crystallization and separate out.Can obtain Ocotillol 624g several times repeatedly, sapogenin content is 96% (HPLC detection), and alkali oxide solution productive rate is 62.4%.Product is colourless needle (dichloromethane-ethanol), mp211-213 ℃ (MeOH), and 10% ethanol solution of sulfuric acid shows purple, Liebermann-Burchard reacting positive.
1H-NMR(300MHz,?C
5D
5N)：0.91(3H,?s,?H-30),?0.96(3H,?s,?H-18),?1.10(3H,?s,?H-19),?1.24(3H,?s,?H-26),?1.25(3H,?s,?H-21),?1.42(3H,?s,?H-28),?1.46(3H,?s,?H-27),?1.97(3H,?s,?H-29),?3.49(1H,?dd,?
J=5.4,?11.1Hz,?H-3),?3.69(1H,?dt,?
J=4.5,?10.4Hz,?H-12),?3.92(1H,?dd,?
J=6.9,?8.3Hz,?H-24),?4.39(1H,?m,?H-6)。
13C-NMR(75MHz,?C
5D
5N)：39.4(C-l),?28.1(C-2),?78.4(C-3),?40.4(C-4),?61.9(C-5),?67.7(C-6),?47.5(C-7),?41.4(C-8),?50.5(C-9),?39.3(C-10),?32.4(C-11),?71.2(C-12),?48.4(C-13),?52.1(C-14),?31.7(C-15),?25.5(C-16),?49.4(C-17),?17.8(C-18),?17.2(C-19),?86.7(C-20),?27.0(C-21),?32.8(C-22),?28.8(C-23),?85.6(C-24),?70.3(C-25),?27.2(C-26),?27.6(C-27),?31.9(C-28),?16.5(C-29),?18.3(C-30)。
Embodiment 5:The preparation of Ocotillol:
F11 is dissolved in the propyl carbinol of dehydration with the anthropomorphic ginseng of 1000g soap, adds 12000ml propyl carbinol sodium.Under the condition of logical oxygen, be heated to 92 ℃, react and stopped in 9 hours.Reaction solution is cooled to room temperature,, discards water layer, the n-butanol layer reclaim under reduced pressure with the saturated washing of propyl carbinol three times.The reaction product of gained is used dissolved in distilled water, and the aqueous solution discards water layer with ethyl acetate extraction three times.Organic layer dehydrates with anhydrous magnesium sulfate, concentrates to obtain oxidation alkaline hydrolysis crude product.Crude product is dissolved with methylene dichloride, filter.Add absolute ethyl alcohol and carry out recrystallization, place post crystallization and separate out.Can obtain Ocotillol 644g several times repeatedly, sapogenin content is 95% (HPLC detection), and alkali oxide solution productive rate is 64.4%.Product is colourless needle (dichloromethane-ethanol), mp211-213 ℃ (MeOH), and 10% ethanol solution of sulfuric acid shows purple, Liebermann-Burchard reacting positive.
1H-NMR(300MHz,?C
5D
5N)：0.91(3H,?s,?H-30),?0.96(3H,?s,?H-18),?1.10(3H,?s,?H-19),?1.24(3H,?s,?H-26),?1.25(3H,?s,?H-21),?1.42(3H,?s,?H-28),?1.46(3H,?s,?H-27),?1.97(3H,?s,?H-29),?3.49(1H,?dd,?
J=5.4,?11.1Hz,?H-3),?3.69(1H,?dt,?
J=4.5,?10.4Hz,?H-12),?3.92(1H,?dd,?
J=6.9,?8.3Hz,?H-24),?4.39(1H,?m,?H-6)。
13C-NMR(75MHz,?C
5D
5N)：39.4(C-l),?28.1(C-2),?78.4(C-3),?40.4(C-4),?61.9(C-5),?67.7(C-6),?47.5(C-7),?41.4(C-8),?50.5(C-9),?39.3(C-10),?32.4(C-11),?71.2(C-12),?48.4(C-13),?52.1(C-14),?31.7(C-15),?25.5(C-16),?49.4(C-17),?17.8(C-18),?17.2(C-19),?86.7(C-20),?27.0(C-21),?32.8(C-22),?28.8(C-23),?85.6(C-24),?70.3(C-25),?27.2(C-26),?27.6(C-27),?31.9(C-28),?16.5(C-29),?18.3(C-30)。
Claims (4)
1. method for preparing Ocotillol, its step is following:
A. get in the propyl carbinol that a pseudo-ginsenoside F 11 is dissolved in dehydration, add 5 ~ 15 times of amount propyl carbinol sodium, under the condition of logical oxygen; Be heated to 80 ~ 100 ℃; React and stopped in about 6 ~ 12 hours, reaction solution is cooled to room temperature, with the saturated washing of propyl carbinol three times; Discard water layer, the n-butanol layer reclaim under reduced pressure;
B. the reaction product of gained is used dissolved in distilled water, the aqueous solution discards water layer with ethyl acetate extraction three times; Organic layer dehydrates with anhydrous magnesium sulfate, concentrates to obtain oxidation alkaline hydrolysis crude product;
C. crude product is dissolved with a small amount of methylene dichloride, filter, add absolute ethyl alcohol and carry out recrystallization, place post crystallization and separate out, can obtain several times repeatedly.
2. preparation method as claimed in claim 1 is characterized in that the pseudo-ginsenoside F 11 solvent temperature is 90-95 ℃ in a step.
3. preparation method as claimed in claim 1 is characterized in that the propyl carbinol add-on is that 8-12 doubly measures in a step.
4. preparation method as claimed in claim 1 is characterized in that the reaction times is 8-10 hour in a step.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569882A (en) * | 2004-04-29 | 2005-01-26 | 上海中药创新研究中心 | Process for preparing protopanoxadiol and protopanaxatriol |
| CN1640406A (en) * | 2004-01-08 | 2005-07-20 | 山东绿叶天然药物研究开发有限公司 | Drug-dropping and intelligence-promoting medicine using ocotillol as effective component, and its preparing method and use |
-
2012
- 2012-01-16 CN CN2012100121609A patent/CN102558271A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640406A (en) * | 2004-01-08 | 2005-07-20 | 山东绿叶天然药物研究开发有限公司 | Drug-dropping and intelligence-promoting medicine using ocotillol as effective component, and its preparing method and use |
| CN1569882A (en) * | 2004-04-29 | 2005-01-26 | 上海中药创新研究中心 | Process for preparing protopanoxadiol and protopanaxatriol |
Non-Patent Citations (2)
| Title |
|---|
| 高璐莎 等: "西洋参茎叶总皂苷氧化裂解的一侧链环合产物", 《沈阳药科大学学报》, vol. 24, no. 09, 20 September 2007 (2007-09-20), pages 552 - 555 * |
| 高璐莎: "西洋参茎叶总皂苷氧化碱解产物研究", 《沈阳药科大学硕士学位论文》, 29 September 2007 (2007-09-29), pages 9 - 24 * |
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Application publication date: 20120711 |