CN102408310B - Method for preparing high-purity solanesol by utilizing prepared opium paste - Google Patents
Method for preparing high-purity solanesol by utilizing prepared opium paste Download PDFInfo
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- CN102408310B CN102408310B CN 201110327408 CN201110327408A CN102408310B CN 102408310 B CN102408310 B CN 102408310B CN 201110327408 CN201110327408 CN 201110327408 CN 201110327408 A CN201110327408 A CN 201110327408A CN 102408310 B CN102408310 B CN 102408310B
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Abstract
The invention discloses a method for preparing high-purity solanesol by utilizing prepared opium paste, which comprises the following steps of: (1) placing the prepared opium paste in acetylation reagent for reaction to obtain prepared opium paste acetylation product; (2) heating and refluxing the prepared opium paste acetylation product for dissolving in organic solvent, filtering the hot reaction solution to remove impurities, taking filter liquor, decompressing and evaporating to dryness to obtain oily matters; (3) adding ethanol and sodium hydroxide to the oily matters for heating, stirring and saponification reaction, after the saponification reaction, cooling the reaction solution, filtering, taking filter liquor, concentrating to obtain concentrated solution, freezing the concentrated solution at low temperature and filtering to obtain crystallized matters; and (4) decolorizing and recrystallizing the crystallized matters to obtain the high-purity solanesol. The method can increase content of free solanesol in the prepared opium paste, the used solvent has low toxicity and the solanesol has high extraction rate and high purity and is easy to realize industrialization production.
Description
Technical field
The concrete a kind of method of extracting Salanesol of the present invention is specifically related to a kind of method of utilizing prepared opium paste to prepare high-purity solanesol.
Background technology
Salanesol is a kind of polyisoprene alcohol, and molecular structural formula is H (CH
2C (CH
3) CHCH
2)
9OH, relative molecular weight are 631, and sterling is white powdery solid, and fusing point is 41 ℃.Salanesol is the Fatty Alcohol(C12-C14 and C12-C18) of long-chain, and low-pole is soluble in organic solvent, and is water insoluble, the certain solubleness of oil in alcoholic solvent.Salanesol is synthesizing coenzyme Q 10 and vitamin K as a kind of important medicine intermediate
2Important source material, this external field of medicaments, its derived product also have the prevention and the treatment cardiovascular and cerebrovascular diseases effect.The existing way of Salanesol in tobacco leaf mainly is two kinds of free state and esterification attitudes, and wherein the Salanesol of free state accounts for 8%, and the Salanesol of esterification attitude accounts for 6%.
The method for preparing Salanesol of announcing at present is a lot, described mode of production general expression adopts the organic solvent of low polarity to extract from tobacco leaf and obtains prepared opium paste, then processes multi-solvents or the extraction of polycomponent mixed solvent multistep through saponification, recrystallization, column chromatography etc. obtain sterling.As number of patent application be 200510111768.7 and number of patent application be to use the resin column chromatography in the method for two patent disclosures such as 2004100067949.X, reagent type is many, operation easier is large.Number of patent application is to have used hexanaphthene, the acetone-multi-solvents such as alcohol in 200410040400.1 the disclosed method of patent in addition, has improved productive rate and content although used saponification process, and the organic solvent kind is numerous, causes difficult solvent recovery.
How to simplify technique, reduce solvent species, and can improve the purity that the extraction yield that extracts Salanesol in the raw material finally improves Salanesol and become the technical problem that needs to be resolved hurrily in this area.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, use the prepared opium paste that utilizes that solvent species is few, the Salanesol extraction yield high, Salanesol purity is high to prepare the method for high-purity solanesol.
Above-mentioned purpose of the present invention realizes by following technique means: a kind of method of utilizing prepared opium paste to prepare high-purity solanesol contains following steps:
(1) after placing acetylation reagent to react prepared opium paste the acetylate of prepared opium paste;
(2) with acetylate reflux dissolving in organic solvent of prepared opium paste, while hot with the reacting liquid filtering removal of impurities, get filtrate and obtain oily matter through evaporated under reduced pressure subsequently;
(3) add ethanol in the oily matter and sodium hydroxide carries out the heated and stirred saponification reaction, saponification reaction is complete gets filtrate with the reaction solution cooled and filtered, after concentrated concentrated solution, with filtering after the concentrated solution cryogenic freezing, get crystallisate;
(4) crystallisate namely obtains highly purified Salanesol behind decolouring, recrystallization.
In above-mentioned steps:
Acetylation reagent described in the step of the present invention (1) is diacetyl oxide, Acetyl Chloride 98Min. or acetic acid, and the temperature of acetylization reaction is that 60 ℃-80 ℃, reaction times are 3-5 hour, and the consumption of acetylation reagent accounts for the 10-15% of prepared opium paste quality.
In the step of the present invention (2) with the acetylate of prepared opium paste in organic solvent in 60 ℃ of-80 ℃ of reflux dissolvings, and the saponification reaction 2 ~ 3 hours of refluxing.
Organic solvent of the present invention is aqueous ethanolic solution, and wherein the volumn concentration of ethanol is 50 ~ 70%, and the consumption of aqueous ethanolic solution is 8 ~ 10 times of prepared opium paste total mass.
Add ethanol in the oily matter in the step of the present invention (3) and sodium hydroxide carried out the heated and stirred saponification reaction 3 ~ 4 hours in 70 ℃ of-80 ℃ of oil baths.
The consumption of ethanol of the present invention accounts for 10-20 times of oily matter total mass, and its volumn concentration is 90 ~ 95%, and the consumption of described sodium hydroxide accounts for 4 ~ 7% of oily matter total mass.
After the saponification reaction reaction solution is filtered after 5 ~ 8 hours in-5 ℃ ~ 0 ℃ cooling in the step of the present invention (3), filtrate is concentrated into after half of original volume to get concentrated solution; Concentrated solution is filtered after freezing 8 ~ 10 hours in-20 ℃ ~-25 ℃, get crystallisate.
The process of crystallisate decolouring is in the step of the present invention (4): crystallisate is placed aqueous ethanolic solution, regulate temperature of reaction and be 80 ℃ and carried out heating reflux reaction 1 ~ 1.5 hour under the effect of gac.
The volumn concentration of wherein said aqueous ethanolic solution is preferably 90%, and its consumption preferably accounts for 8 ~ 15 times of crystallisate total mass, and the consumption of gac preferably accounts for 4% ~ 6% of crystallisate quality.
In the step of the present invention (4) during crystallization-20 ℃ ~-25 ℃ freezing and crystallizings 8 ~ 10 hours, namely get purity and be higher than 90% Salanesol.
Compared with prior art, the present invention has following beneficial effect:
(1) prepared opium paste removal of impurities after acetylize is processed can improve yield and the content of Salanesol again among the present invention after purification is processed in saponification;
(2) solvent species that adopts among the present invention is less, and it is simple to reclaim reagent;
(3) integrated artistic of the present invention is simple, and is with short production cycle;
(4) preparation method's of the present invention production technique cost is low, is easy to realize suitability for industrialized production, and the purity of the Salanesol that employing the inventive method prepares reaches more than 90%.
Embodiment
Below the invention will be further described, but embodiments of the present invention are not limited to following embodiment introduction, all variation that is equal to or flexible categories that all should be considered as the present invention's protection of doing according to method of the present invention.Below raw materials used, except special indicating, be commercially available.
Embodiment 1
To be restrained in the acetylation reagent diacetyl oxide by the prepared opium paste 100 that tobacco leaf obtains through No. six solvent extractions and concentrated dried solvent and react, the temperature of reaction is that 60 ℃, reaction times are 3.5 hours, and the consumption of diacetyl oxide is 11 grams.Add the ethanolic soln of 900 grams 55% in the acetylate after reaction finishes and dissolve in 60 ℃ of reflux, return time is 2 hours.Subsequently filtered while hot removal of impurities, last evaporated under reduced pressure filtrate obtain oily matter 78.6 grams.Add 1200 gram concentration in the oily matter and be 90% ethanolic soln and 4.7 gram sodium hydroxide, mixture was in 70 ℃ of heated and stirred saponification of oil bath 3 hours, react complete afterreaction liquid in-5 ℃ of coolings 6 hours, filtering and impurity removing, mother liquid obtained be evaporated to half volume with concentrated solution after-20 ℃ filter after freezing 9 hours and obtain light yellow crystallisate 15.6 grams, the crystallisate heating is dissolved in 165 grams, 90% ethanolic soln, add subsequently 0.7 gram gac, 80 ℃ of backflows were filtered after 1.5 hours, filtrate is freezing 8 hours in-20 ℃, filtration obtains 11.3 gram Salanesols, and measuring Salanesol content through HPLC is 92.12%.
Embodiment 2
To be restrained in acetylation reagent by the prepared opium paste 100 that tobacco leaf obtains through No. six solvent extractions and concentrated dried solvent and react, the temperature of acetylization reaction is that 70 ℃, reaction times are 4 hours, and the consumption of diacetyl oxide is 13 grams.Add the ethanolic soln of 800 grams 70% in the acetylate after reaction finishes and dissolve in 70 ℃ of reflux, return time is 2.5 hours.Subsequently filtered while hot removal of impurities, last evaporated under reduced pressure filtrate obtain oily matter 80.7 grams.Past oily matter adding 1200 gram concentration are 90% ethanolic soln and 4.8 gram sodium hydroxide, mixture was in 75 ℃ of heated and stirred saponification of oil bath 3.5 hours, react complete afterreaction liquid in-5 ℃ of coolings 6 hours, filtering and impurity removing, mother liquid obtained be evaporated to half volume with concentrated solution after-20 ℃ filter after freezing 8 hours and obtain light yellow crystallisate 16.4 grams, the crystallisate heating is dissolved in 160 grams, 90% ethanolic soln, add subsequently 0.8 gram gac, 80 ℃ of backflows were filtered after 1 hour, filtrate is freezing 8 hours in-20 ℃, filtration obtains 10.2 gram Salanesols, and measuring Salanesol content through HPLC is 91.23%.
Embodiment 3
To be restrained in acetylation reagent by the prepared opium paste 100 that tobacco leaf obtains through No. six solvent extractions and concentrated dried solvent and react, the temperature of acetylization reaction is that 80 ℃, reaction times are 5 hours, and the consumption of diacetyl oxide is 15 grams.Add the ethanolic soln of 1000 grams 60% in the acetylate after reaction finishes and dissolve in 80 ℃ of reflux, return time is 3 hours.Subsequently filtered while hot removal of impurities, last evaporated under reduced pressure filtrate obtain oily matter 76.7 grams.Past oily matter adding 1534 gram concentration are 90% ethanolic soln and 4.7 gram sodium hydroxide, mixture was in 80 ℃ of heated and stirred saponification of oil bath 4 hours, react complete afterreaction liquid in-4 ℃ of coolings 8 hours, filtering and impurity removing, mother liquid obtained be evaporated to half volume with concentrated solution after-10 ℃ filter after freezing 10 hours and obtain light yellow crystallisate 15.8 grams, the crystallisate heating is dissolved in 237 grams, 90% ethanolic soln, add subsequently 0.8 gram gac, 80 ℃ of backflows were filtered after 1.5 hours, filtrate is freezing 10 hours in-25 ℃, filtration obtains 10.9 gram Salanesols, and measuring Salanesol content through HPLC is 92.43%.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (2)
1. method of utilizing prepared opium paste to prepare high-purity solanesol is characterized in that containing following steps:
(1) after placing acetylation reagent to react prepared opium paste the acetylate of prepared opium paste;
(2) with acetylate reflux dissolving in organic solvent of prepared opium paste, while hot with the reacting liquid filtering removal of impurities, get filtrate and obtain oily matter through evaporated under reduced pressure subsequently;
(3) add ethanol in the oily matter and sodium hydroxide carries out the heated and stirred saponification reaction, saponification reaction is complete gets filtrate with the reaction solution cooled and filtered, after concentrated concentrated solution, with filtering after the concentrated solution cryogenic freezing, get crystallisate;
(4) crystallisate namely obtains highly purified Salanesol behind decolouring, recrystallization;
Acetylation reagent described in the step (1) is diacetyl oxide, Acetyl Chloride 98Min. or acetic acid, and the temperature of acetylization reaction is that 60 ℃-80 ℃, reaction times are 3-5 hour, and the consumption of acetylation reagent accounts for the 10-15% of prepared opium paste quality.
2. the method for utilizing prepared opium paste to prepare high-purity solanesol according to claim 1 is characterized in that: in the step (2) with the acetylate of prepared opium paste in organic solvent in 60 ℃ of-80 ℃ of reflux dissolvings, and the saponification reaction 2 ~ 3 hours of refluxing.
3. the method for utilizing prepared opium paste to prepare high-purity solanesol according to claim 2, it is characterized in that: described organic solvent is aqueous ethanolic solution, and wherein the volumn concentration of ethanol is 50 ~ 70%, and the consumption of aqueous ethanolic solution is 8 ~ 10 times of prepared opium paste total mass.
4. the method for utilizing prepared opium paste to prepare high-purity solanesol according to claim 1 is characterized in that: add ethanol in the oily matter in the step (3) and sodium hydroxide carried out the heated and stirred saponification reaction 3 ~ 4 hours in 70 ℃ of-80 ℃ of oil baths.
5. the method for utilizing prepared opium paste to prepare high-purity solanesol according to claim 4, it is characterized in that: the consumption of described ethanol accounts for 10-20 times of oily matter total mass, its volumn concentration is 90 ~ 95%, and the consumption of described sodium hydroxide accounts for 4 ~ 7% of oily matter total mass.
6. the method for utilizing prepared opium paste to prepare high-purity solanesol according to claim 1 is characterized in that: after the saponification reaction reaction solution is filtered after 5 ~ 8 hours in-5 ℃ ~ 0 ℃ cooling in the step (3), filtrate is concentrated into after half of original volume to get concentrated solution; Concentrated solution is filtered after freezing 8 ~ 10 hours in-20 ℃ ~-25 ℃, get crystallisate.
7. the method for utilizing prepared opium paste to prepare high-purity solanesol according to claim 1, it is characterized in that: the process of crystallisate decolouring is in the step (4): crystallisate is placed aqueous ethanolic solution, regulate temperature of reaction and be 80 ℃ and carried out heating reflux reaction 1 ~ 1.5 hour under the effect of gac.
8. the method for utilizing prepared opium paste to prepare high-purity solanesol according to claim 7, it is characterized in that: the volumn concentration of described aqueous ethanolic solution is 90%, its consumption accounts for 8 ~ 15 times of crystallisate total mass, and the consumption of gac accounts for 4% ~ 6% of crystallisate quality.
9. the method for utilizing prepared opium paste to prepare high-purity solanesol according to claim 1 is characterized in that: in the step (4) during crystallization-20 ℃ ~-25 ℃ freezing and crystallizings 8 ~ 10 hours, namely get purity and be higher than 90% Salanesol.
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| CN 201110327408 CN102408310B (en) | 2011-10-25 | 2011-10-25 | Method for preparing high-purity solanesol by utilizing prepared opium paste |
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| CN 201110327408 CN102408310B (en) | 2011-10-25 | 2011-10-25 | Method for preparing high-purity solanesol by utilizing prepared opium paste |
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| CN102408310A CN102408310A (en) | 2012-04-11 |
| CN102408310B true CN102408310B (en) | 2013-10-30 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676502A (en) * | 2004-04-03 | 2005-10-05 | 杨群力 | Solanesol refining method |
| CN101940361A (en) * | 2010-10-11 | 2011-01-12 | 广东中烟工业有限责任公司 | Processing method of waste tobacco |
| CN101979613A (en) * | 2010-10-28 | 2011-02-23 | 西北师范大学 | Ultrasound enzyme-assisted solanesol extracting method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4013731A (en) * | 1969-04-24 | 1977-03-22 | Nisshin Flour Milling Co., Ltd. | Process for the manufacture of solanesol |
| CN101284766B (en) * | 2008-06-04 | 2010-04-21 | 云南瑞升烟草技术（集团）有限公司 | Process for finely purifying high-purity solanesol form coarse cream of solanesol |
| CN101935269B (en) * | 2010-09-30 | 2013-06-12 | 长安大学 | Method for precipitating, separating and purifying solanesol |
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2011
- 2011-10-25 CN CN 201110327408 patent/CN102408310B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676502A (en) * | 2004-04-03 | 2005-10-05 | 杨群力 | Solanesol refining method |
| CN101940361A (en) * | 2010-10-11 | 2011-01-12 | 广东中烟工业有限责任公司 | Processing method of waste tobacco |
| CN101979613A (en) * | 2010-10-28 | 2011-02-23 | 西北师范大学 | Ultrasound enzyme-assisted solanesol extracting method |
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