CN1260243C - Method for preparing sitostamol - Google Patents
Method for preparing sitostamol Download PDFInfo
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- CN1260243C CN1260243C CN 200410041312 CN200410041312A CN1260243C CN 1260243 C CN1260243 C CN 1260243C CN 200410041312 CN200410041312 CN 200410041312 CN 200410041312 A CN200410041312 A CN 200410041312A CN 1260243 C CN1260243 C CN 1260243C
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- stigmasterol
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Abstract
The present invention discloses a method for preparing sitostamol, which relates to a method for preparing sitostamol from stigmasterol through catalytic hydrogenation. The preparation method uses specific organic solvent as a reaction medium, and uses Pd/carbon as a catalyst. Hydrogen gas is supplied under normal pressure or low pressure to catalyze and hydrogenate stigmasterol to prepare sitostamol. The present invention provides process conditions for preparing the sitostamol from the stigmasterol by catalytic hydrogenation. The preparation method has the advantages of simple process and convenient operation. Reaction is carried out under normal pressure or low pressure, and the industrial production of a product is easy to realize. The preparation method does not use sitosterol having high price and difficult obtainment, and adopts the stigmasterol having low price and easy obtainment at home as a raw material. The preparation cost of the sitostamol is markedly lowered.
Description
Technical field
A kind of preparation method of sitostanol relates to by the Stigmasterol catalytic hydrogenation and prepares sitostanol.
Background technology
Sterol extensively is present in eukaryotic cell, and it is the fundamental component that constitutes animal and plant cells, extensively exists in animals and plants.At occurring in nature, plant sterol mainly exists with Stigmasterol, Sitosterol, campesterol and saturated plant sterol forms such as (being stanols).Sitosterol, sitostanol are mainly used in food, are used for reducing blood-fat in the west, and its decreasing cholesterol performance is very remarkable, and some animals and clinical study think that sitostanol is suppressing more effective than Sitosterol on cholesterol absorption and the reducing cholesterol concentration.Stanols is few in occurring in nature quantity, mainly the unsaturated double-bond of sterol is reduced into saturated bond by catalytic hydrogenation, plant sterol is transformed into corresponding stanols by hydrogenation, at present external sitostanol (sitostanol) is that raw material catalytic hydrogenation under certain pressure makes with the Sitosterol, as U.S. Pat: 20020045773, US:20030004361, US:6 147 235, and domestic still do not have sitostanol production.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of sitostanol is a raw material with the domestic Stigmasterol that is easy to get (stigmasterol), by normal pressure or low pressure catalytic hydrogenation, makes the sitostanol of higher degree.
Technical scheme of the present invention:
Reaction scheme:
With the specific organic solvent is reaction medium, is catalyzer with palladium/charcoal, logical at atmospheric or low pressure hydrogen catalytic hydrogenation Stigmasterol, preparation sitostanol.With the high effective liquid chromatography for measuring reaction solution, calculate reaction conversion ratio.
The transformation efficiency definition:
X (sitostanol)=n
Sitostanol(the real mol that gets)/n
Sitostanol(theoretical mol)
The wherein theoretical amount (mol) that can get is calculated with 100% Stigmasterol and is obtained, and the actual amount (mol) that obtains obtains after by the high-performance liquid chromatogram determination reaction solution.
The reaction conversion ratio measuring method: analytical column be the InertsilC8 post (5 μ m, 4.6 * 250mm), column temperature is 25 ℃, detector is a Knauer RI K2301 differential refraction detector, moving phase is acetonitrile, flow velocity is 1ml/min.
Reaction solvent is to the influence of transformation efficiency
Under temperature of reaction was 78～82 ℃, the catalytic hydrogenation condition of Pd/C consumption 0.1%, the reaction times, the differential responses solvent saw Table 1 to the influence of sitostanol transformation efficiency when being 8h.
Table 1 reaction solvent is to the influence of transformation efficiency
| Solvent | Transformation efficiency/% |
| 1,2-PD ethanol n-butanol isopropyl alcohol benzene toluene dimethylbenzene oxolane benzinum | 5.25 76.70 87.43 94.85 85.64 87.41 84.23 76.41 81.90 |
As shown in Table 1, different solvents is bigger to the reaction conversion ratio influence, when being reaction medium with Virahol etc., the product sitostanol has higher transformation efficiency, is reaction solvent so the present invention selects Virahol, propyl carbinol, ethanol, benzene,toluene,xylene, tetrahydrofuran (THF) or sherwood oil.
Temperature of reaction is to the influence of transformation efficiency
With the Virahol is solvent, under the catalytic hydrogenation condition of Pd/C consumption 0.1%, reaction times is when being 8h, temperature of reaction has a significant effect to reaction conversion ratio, raise with temperature of reaction, the transformation efficiency of product sitostanol increases, this speed that shows Stigmasterol hydro-reduction under comparatively high temps improves, temperature of reaction is greater than after 60 ℃, the raising of this speed eases up, consider the difference of Virahol organic solvent boiling point in addition, so selective reaction temperature of the present invention is 60-90 ℃, the temperature of reaction when selecting Virahol or ethanol for use is consistent with their boiling temperature, promptly 82 ℃ or 78 ℃, be convenient to production control.
Proportioning raw materials is to the influence of transformation efficiency
Temperature of reaction is under 82 ℃, the catalytic hydrogenation condition of Pd/C consumption 0.1%, reaction times is when being 8h, investigate the influence of n (Virahol): n (Stigmasterol) to transformation efficiency, increase with Stigmasterol, the transformation efficiency of sitostanol obviously descends, increase the amount of Virahol, transformation efficiency increases, consider that material concentration is crossed and low can reduce production efficiency and increase production cost, the present invention selects n (organic solvent): n (Stigmasterol)=20-80 for use: 1, and ratio is n (organic solvent): n (Stigmasterol)=60-80 preferably: 1.
Catalyst levels is to the influence of transformation efficiency
Temperature of reaction is 82 ℃, under the catalytic hydrogenation condition of n (Virahol): n (Stigmasterol)=80: 1, reaction times is when being 8h, investigate of the influence of Pd/C consumption to transformation efficiency, catalyst levels has a significant effect to transformation efficiency, catalyst levels is from 0.05%, increase with catalyst levels, the transformation efficiency of sitostanol obviously improves, catalyst levels was greater than 0.2% o'clock, transformation efficiency tends towards stability, so the massfraction that selecting catalyst consumption of the present invention is a palladium is the 0.05%-0.3% of Stigmasterol, catalyst levels preferably: the massfraction of palladium is the 0.1%-0.2% of Stigmasterol.
Reaction times is to the influence of transformation efficiency
Reaction times has a significant effect to transformation efficiency, increases with the reaction times, and the transformation efficiency of sitostanol obviously improves, and when reaction times during greater than 6h, transformation efficiency tends towards stability, so the selective reaction time of the present invention is 6-12h, the reaction times is 8-10 hour preferably.
Catalyzer is reused the influence to transformation efficiency
Catalyzer is reused does not have obvious influence to transformation efficiency.
Table 2 catalyzer is reused the influence of number of times to transformation efficiency
| Access times | ||||||
| 1 | 2 | 3 | 4 | 5 | 20 | |
| Transformation efficiency/% | 94.85 | 94.28 | 94.12 | 94.53 | 94.66 | 94.02 |
Reaction pressure is to the influence of transformation efficiency
Reaction pressure increases, and transformation efficiency can increase.In industrial production, adopt higher reaction pressure to drop into by increase equipment, be not easy to production operation, so the present invention adopts normal pressure or low pressure reaction condition, promptly reaction pressure is 101 kPas-1010 kPas (1-10atm).
During catalyzed reaction, hydrogen feeding amount is 200-350ml/min under normal pressure, is to pass to required reaction pressure in encloses container under the low pressure.
In sum, the present invention is reaction medium with the specific organic solvent, with palladium/charcoal is catalyzer, logical at atmospheric or low pressure hydrogen catalytic hydrogenation Stigmasterol, the preparation sitostanol, catalyst levels: the massfraction of palladium is the 0.05%-0.3% of Stigmasterol, organic solvent: the Stigmasterol mol ratio is 20-80: 1, temperature of reaction: 60-90 ℃, reaction pressure: 101 kPas-1010 kPas, reaction times: 6-12 hour, react the after-filtration that finishes, white solid is separated out in the filtrate cooling, gets the product sitostanol.
Beneficial effect of the present invention
(1) by of the influence of each reaction conditions of research to product yield, determined that the Stigmasterol catalytic hydrogenation prepares the processing condition of sitostanol, the molar yield of sitostanol is 95.71%, the product purity height, sitostanol purity is about 94.92%, meets the foodstuffs industry service requirements.
(2) reaction is carried out at atmospheric or low pressure, and the suitability for industrialized production of product is simple.
(3) selecting Stigmasterol for use is raw material, has significantly reduced the preparation cost of sitostanol.It is raw material that external technology all adopts Sitosterol, and the Sitosterol of domestic higher degree costs an arm and a leg, and in September, 2003, domestic Sitosterol price was three times of Stigmasterol, and supply is few, the Stigmasterol that the present invention has selected for use and domesticly has been easy to get, price is lower is a raw material, greatly reduces material cost.
Embodiment
Embodiment 1
Be equipped with and add reaction solvent Virahol 250ml (3.2mol), 10%Pd/C catalyst levels in three mouthfuls of glass flask of reflux condensing tube: be 0.2% (336.8mg) of Stigmasterol, be warming up to 65 ℃, stir down and feed hydrogen, air flow is 350ml/min, insulation activation 0.5h.Be warming up to 82 ℃, add Stigmasterol 16.84g (0.04mol), 101 kPas of reaction pressures, reaction 10h, reaction conversion ratio 95.71%.The 10%Pd/C catalyzer: industrial goods, Changzhou Ke Feng chemical reagent factory produces.
Embodiment 2
Reaction medium adopts ethanol, and 78 ℃ of temperature of reaction, all the other conditions be with embodiment 1, reaction conversion ratio 86.30%.
Embodiment 3
Reaction medium adopts propyl carbinol, and 90 ℃ of temperature of reaction, all the other conditions be with embodiment 1, reaction conversion ratio 92.23%.
Embodiment 4
Reaction medium adopts benzene, and 80 ℃ of temperature of reaction, all the other conditions be with embodiment 1, reaction conversion ratio 90.67%.
Embodiment 5
Reaction medium adopts toluene, and 90 ℃ of temperature of reaction, all the other conditions be with embodiment 1, reaction conversion ratio 91.78%.
Embodiment 6
Reaction medium adopts dimethylbenzene, and 90 ℃ of temperature of reaction, all the other conditions be with embodiment 1, reaction conversion ratio 92.01%.
Embodiment 7
Reaction medium adopts tetrahydrofuran (THF), and 60 ℃ of temperature of reaction, all the other conditions be with embodiment 1, reaction conversion ratio 82.71%.
Embodiment 8
Reaction medium adopts sherwood oil, and 60 ℃ of temperature of reaction, all the other conditions be with embodiment 1, reaction conversion ratio 83.11%.
Embodiment 9
In airtight pressure-resistant reaction vessel, catalyst levels: the massfraction of palladium is 0.05% of a Stigmasterol, Virahol: the Stigmasterol mol ratio is 20: 1, feed hydrogen, making reaction pressure is 1010 kPas, and control reaction temperature is 60 ℃, reaction times 8h, all the other conditions are with embodiment 1, reaction conversion ratio 82.89%.
Embodiment 10
Catalyst levels: the massfraction of palladium is 0.3% of a Stigmasterol, Virahol: the Stigmasterol mol ratio is 80: 1,82 ℃ of temperature of reaction, and reaction times 6h, all the other conditions are with embodiment 1, reaction conversion ratio 92.99%.
Embodiment 11
Catalyst levels: the massfraction of palladium is 0.05% of a Stigmasterol, Virahol: the Stigmasterol mol ratio is 20: 1,60 ℃ of temperature of reaction, and reaction times 12h, all the other conditions are with embodiment 1, reaction conversion ratio 78.41%.
Embodiment 12
In airtight pressure-resistant reaction vessel, catalyst levels: the massfraction of palladium is 0.1% of a Stigmasterol, Virahol: the Stigmasterol mol ratio is 60: 1, feed hydrogen, making reaction pressure is 1010 kPas, and control reaction temperature is 80 ℃, reaction times 8h, all the other conditions are with embodiment 1, reaction conversion ratio 93.74%.
Embodiment 13
The air flow of hydrogen is 200ml/min, and all the other conditions are with embodiment 1, reaction conversion ratio 92.71%.
Claims (7)
1. the preparation method of a sitostanol, it is characterized in that with the specific organic solvent being reaction medium, with palladium/charcoal is catalyzer, logical at atmospheric or low pressure hydrogen catalytic hydrogenation Stigmasterol, the preparation sitostanol, catalyst levels: the massfraction of palladium is the 0.05%-0.3% of Stigmasterol, organic solvent: the Stigmasterol mol ratio is 20-80: 1, temperature of reaction: 60-90 ℃, reaction pressure: 101 kPas-1010 kPas, reaction times: 6-12 hour, react the after-filtration that finishes, white solid is separated out in the filtrate cooling, gets the product sitostanol;
Organic solvent as reaction medium adopts Virahol, propyl carbinol, ethanol, benzene,toluene,xylene, tetrahydrofuran (THF) or sherwood oil.
2. preparation method according to claim 1, logical hydrogen in reaction medium wherein: the reaction medium that will place catalyzer before the logical hydrogen earlier is warmed up to 65 ℃, deactivated catalyst 0.5 hour adopts the synthesis under normal pressure condition, and the hydrogen air flow is 200-350ml/min; Or adopt the low pressure reaction condition, then in closed reactor, lead to hydrogen to required reaction pressure.
3. preparation method according to claim 1, the massfraction of catalyst levels palladium wherein is the 0.1%-0.2% of Stigmasterol.
4. preparation method according to claim 1, organic solvent wherein: the Stigmasterol mol ratio is 60-80: 1.
5. preparation method according to claim 1, temperature of reaction wherein: 78-82 ℃.
6. preparation method according to claim 1, reaction pressure wherein: 101 kPas.
7. preparation method according to claim 1, reaction times wherein: 8-10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410041312 CN1260243C (en) | 2004-07-06 | 2004-07-06 | Method for preparing sitostamol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410041312 CN1260243C (en) | 2004-07-06 | 2004-07-06 | Method for preparing sitostamol |
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| CN1594351A CN1594351A (en) | 2005-03-16 |
| CN1260243C true CN1260243C (en) | 2006-06-21 |
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| CN 200410041312 Expired - Fee Related CN1260243C (en) | 2004-07-06 | 2004-07-06 | Method for preparing sitostamol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010010228A1 (en) * | 2008-07-25 | 2010-01-28 | Raisio Nutrition Ltd | Effective hydrogenation process |
| CN102407108A (en) * | 2011-10-13 | 2012-04-11 | 南京大学连云港高新技术研究院 | Palladium catalyst loaded by mesoporous carbon as well as preparation method and application thereof |
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