CN1202490A - Process for preparing high content d-alpha type vitamin E - Google Patents
Process for preparing high content d-alpha type vitamin E Download PDFInfo
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- CN1202490A CN1202490A CN98102350A CN98102350A CN1202490A CN 1202490 A CN1202490 A CN 1202490A CN 98102350 A CN98102350 A CN 98102350A CN 98102350 A CN98102350 A CN 98102350A CN 1202490 A CN1202490 A CN 1202490A
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- tocopherol
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Natural matter extract liquid containing total tocopherol more than 58% and formaldehyde as methylating agent produce methylation reaction in the presence of catalyst including chloride of Zn, Sb, etc.as well as lewis acid and boron-level isoproton acid; solvent monohydric or dihydric alcohol or ketone and reducatnat Sn, Zn and other elements at 70-120 deg.c to produce d-alpha type vitamin E with content over 90%. Supercritical CO2 extraction process at 40-80 deg.c temperature and 20-30 MPa pressure is also adopted. The solvent, the catalyst and CO2 are reused.
Description
The present invention relates to a kind of method for preparing high content d-alpha type vitamin E, particularly relate to a kind of methylating and prepare the method for high content d-alpha type vitamin E from non-d-alpha-tocopherol.
Natural VE (VitamanE) is a kind of mixture by 4 kinds of tocopherol homologues, and its structural formula is as follows:
| Title | ???R1 | ???R2 | ???R3 | |
| D-alpha-tocopherol (5,7,8, the trimethylammonium tocopherol) | ???CH 3 | ???CH 3 | ???CH 3 | |
| Non-D-alpha-tocopherol | D-β tocopherol (5,8 dimethyl tocopherol) | ???CH 3 | ???H | ???CH 3 |
| D-gama tocopherol (7,8 dimethyl tocopherol) | ???H | ???CH 3 | ???CH 3 | |
| D-methyltocol (8 dimethyl tocopherol) | ???H | ???H | ???CH 3 | |
In the said structure of tocopherol,, very high medicinal, nutritive value and economic worth are arranged with tool biological activity of d-alpha-tocopherol and application security.But in as the natural tocopherol resource d-alpha-tocopherol content very low, generally only below 10%.The structure of non-d-alpha-tocopherol as can be seen, non-d-alpha-tocopherol is only than d-alpha-tocopherol few one or two methyl on aromatic hydrocarbons 5,7 positions.Therefore, pass through chemical method---methylation reaction, realize by of the conversion of non-d-alpha-tocopherol to the d-alpha-tocopherol.Simultaneously, non-d-alpha-tocopherol still has the inorganic and organic impurity of part in the d-alpha-tocopherol product after methylating, must remove as medicine and healthcare products.
From the fifties so far, reported in literature many about produce the method for d-alpha-tocopherol by dissimilar methylation reactions by non-d-alpha-tocopherol.As us-2,834,604, us-3,819,657, Ri Tekaiping 9-124635 etc.And the transformation efficiency that the general obvious problem that exists of these methods is a methylation reaction is not high enough, and reduction technique equipment requires harshness relatively, and equipment corrosion is serious, and process is difficult to maintain techno-economic effect preferably, and industrialization is difficulty etc. relatively.
The object of the present invention is to provide a kind of transformation efficiency height that methylates, equipment requirements is not high, and equipment corrosion is light, and industrialization is easy to new methylation method.Cooperate the method that adopts supercritical extraction technique to prepare the high content d-alpha tocopherol.
Embodiment of the present invention are as follows:
Methylation method:
(1) adopt the non-d-alpha-tocopherol strong solution of extracting by natural goods, total tocopherol content 〉=58%,
(2) methylating agent of non-d-alpha-tocopherol enriched material should be oxygenatedchemicalss such as aldehydes, generally can adopt formalin, the formaldehyde tripolymer, and Paraformaldehyde 96 etc.,
(3) catalyzer of methylation reaction is AlCl
3, SnCl
2, ZnCl
2, FeCl
3Deng Lewis acid, protonic acids such as boric acid, hydrochloric acid, ortho-phosphoric acid and monobasic, di-carboxylic acid,
(4) Fan Ying solvent is monobasic and dibasic alcohol, ether, ketone, acid and normal alkane, aromatic hydrocarbons etc.,
(5) with than active metal tin, zinc is the reaction reductive agent,
(6) temperature of reaction is in 70-120 ℃ of scope,
(7) carry out supercritical CO
2Extraction, temperature is 40-80 ℃, pressure is 20-30Mpa.
Following preferential example elaborates to the present invention, but does not mean that limitation of the scope of the invention:
Example 1, with non-d-alpha-tocopherol enriched material 150 gram (tocopherol total contents 72.1%, d-alpha-tocopherol 6.81%), formalin 59.6 gram (concentration of formaldehyde 38.5%) zinc one tin composite powder 75.6 grams (effective metal total content＞98%), zinc, muriate 7.4 grams of tin, Glacial acetic acid 175 grams, boric acid 10 grams, ethylene glycol 60 grams mix dissolving in the lump in 1000 milliliters of reaction flasks under the normal temperature, progressively be warming up to 80 ℃ ± 2 ℃, keep refluxing, continue reaction 5.5 hours, reaction finishes, be cooled to below 40 ℃, reaction soln is washed with water, filter, separate, obtain elementary enriched material 143 grams (the tocopherol total content is 72.3%, and wherein d-alpha-tocopherol content is 70.2%) of d-alpha-tocopherol.Continuation is at 55 ± 5 ℃, and 25 ± 5MPa pressure adopts CN-to finish supercritical CO down
2Extraction finally obtains high d-α type tocopherol 80.2 grams (the tocopherol total content is 95.5%, and d-alpha-tocopherol content is 90.5%).The catalyzer of process, solvent all are able to reuse, supercritical CO
2Recycle, total recovery rate of tocopherol is 93%.
Example 2, remove methylating agent and adopt formaldehyde tripolymer 25 grams, it is 7.6 grams that catalyzer adopts the muriate of aluminium, iron, solvent is acetone 60 grams, temperature changes into outside 100 ± 2 ℃, all the other conditions are identical with example 1, and (the tocopherol total content is 74.2%, and wherein d-alpha-tocopherol content is 70.5% with the identical supercritical CO of example 1 to obtain the elementary enriched material of d-alpha-tocopherol 140 grams
2Obtain high d-alpha-tocopherol under the extraction conditions, (the tocopherol total content is 95.2% to 79 grams, and d-alpha-tocopherol phenol content is 90.8%, and total recovery rate of tocopherol is 92.5%.
The major advantage of the inventive method is:
(1) is converted in the methylation reaction of d-alpha tocopherol the one-step technology that adopts the reduction of methylolation and methylol intermediate to finish simultaneously at the non-d-alpha tocopherol of enforcement.
(2) the methylolation intermediate is reduced to methide and has adopted non-pressure process, does not use high-pressure hydrogenation to be beneficial to industrialization.
(3) used supercritical CO2Novel extraction technology is concentrated to the d-alpha tocopherol, and purifying obtains high-quality high d-α type tocopherol.
Claims (1)
1. one kind prepares the method for high content d-alpha type vitamin E from non-d-alpha-tocopherol, it is characterized in that:
(1) adopt the non-d-alpha-tocopherol strong solution of extracting by natural goods, total tocopherol content 〉=58%,
(2) methylating agent of non-d-alpha-tocopherol enriched material should be oxygenatedchemicalss such as aldehydes, generally can adopt formalin, the formaldehyde tripolymer, and Paraformaldehyde 96 etc.,
(3) catalyzer of methylation reaction is AlCl
3, SnCl
2, ZnCl
2, FeCl
3Deng Lewis acid, protonic acids such as boric acid, hydrochloric acid, ortho-phosphoric acid and monobasic, di-carboxylic acid,
(4) Fan Ying solvent is monobasic and dibasic alcohol, ether, ketone, acid and normal alkane, aromatic hydrocarbons etc.,
(5) with than active metal tin, zinc is the reaction reductive agent,
(6) temperature of reaction is in 70-120 ℃ of scope,
(7) carry out supercritical CO
2Extraction, temperature is 40-80 ℃, pressure is 20-30Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102350A CN1202490A (en) | 1998-06-08 | 1998-06-08 | Process for preparing high content d-alpha type vitamin E |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102350A CN1202490A (en) | 1998-06-08 | 1998-06-08 | Process for preparing high content d-alpha type vitamin E |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1202490A true CN1202490A (en) | 1998-12-23 |
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ID=5217282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98102350A Pending CN1202490A (en) | 1998-06-08 | 1998-06-08 | Process for preparing high content d-alpha type vitamin E |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1202490A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153102A (en) * | 2015-09-30 | 2015-12-16 | 宜春大海龟生命科学有限公司 | Method for using mixed tocopherol as raw material to prepare alpha-tocopherol |
-
1998
- 1998-06-08 CN CN98102350A patent/CN1202490A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153102A (en) * | 2015-09-30 | 2015-12-16 | 宜春大海龟生命科学有限公司 | Method for using mixed tocopherol as raw material to prepare alpha-tocopherol |
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