CN101285088A - Synthetic method of soya-bean oil monoester derivates of vitamin A - Google Patents
Synthetic method of soya-bean oil monoester derivates of vitamin A Download PDFInfo
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- CN101285088A CN101285088A CNA2008101238632A CN200810123863A CN101285088A CN 101285088 A CN101285088 A CN 101285088A CN A2008101238632 A CNA2008101238632 A CN A2008101238632A CN 200810123863 A CN200810123863 A CN 200810123863A CN 101285088 A CN101285088 A CN 101285088A
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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
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Abstract
The invention discloses a method for synthesizing a soybean oil monoester derivative of vitamin A, which comprises the following steps that: (1) at the temperature of between 4 and 60 DEG C, a three-necked bottle filled with vitamin A solution with concentration of between 8 and 12 percent is wrapped by silver paper and keeps out of the sun; (2) soybean oil is added into the three-necked bottle, the weight ratio of soybean oil and the vitamin A is 0.8-1: 1, and an electric stirrer with the rotating speed of between 50 and 400rpm is used to stir; (3) lipase is added into the soybean oil according to the proportion that: soybean oil is between 1g:1ml and 1g:32ml; (4) the mixture is stirred to react under constant temperature until the needed product is obtained. The invention takes the lipase as catalyst to perform the enzyme method mono-esterification of the vitamin A through an ester exchange reaction, and the soybean oil in the system is a reactant and also is reaction solvent at the same time, thereby reducing organic waste liquid, being economic and environment-friendly, and having high reaction yield and recoverable catalyst.
Description
Technical field
The present invention relates to the synthetic method of the soya-bean oil monoester derivates of vitamin A, belong to the Application Areas of enzyme in medicine is synthetic.
Background technology
Vitamin A and derivative thereof all have wide commercial promise at cosmetic field and field of medicaments.The chemistry of vitamin A is called Vogan-Neu, is found the earliest VITAMIN.Vitamin A has two kinds, and a kind of is retinol (retionl), is initial vitamin A form (only being present in the animal food); Another kind is carotene (carotene), changes the preformation material (provitaminA can absorb from vegetalitas and animality things) of vitamin A in vivo into.
Before more than 1000 years, the far away animal livers of putting down in writing in " prescriptions worth thousand gold " of the Sun Si Tang Dynasty can be treated nyctalopia.1913,4 scientists such as U.S. Davis found that Oils,glyceridic,cod-liver can be cured xeropthalmus.And a kind of yellow thick liquid of from Oils,glyceridic,cod-liver, purifying out, nineteen twenty Britain scientist Man Ete is a vitamin A with its definite designation.Formally vitamin A is regarded as the necessary factor in the nutrition in the world, can be caused nyctalopia after the shortage.
Vitamin A is a unsaturated monohydroxy-alcohol with ester ring, and its structural formula is as follows:
Although it is water-soluble bad, but vitamin A still has different physiological roles, it can accelerate Normocellular growth, for keeping healthy epithelium and stoping the diffusion of skin carcinoma to be very important by stimulating normal cell to break up, simultaneously, it also all is essential to the growth of eyesight, growth, epithelium and bone, the generation and the growing of fetus of sperm.
But vitamin A itself has a lot of deficiencies.At first, it is a lot of to the side effect that human body produces, and skin is had pungency.Therefore, many times people have to take other drug and treat or suppress these side effects.In addition, vitamin A self is also very unstable, its meeting slow oxidation in air, and under UV-irradiation, lose activity.Simultaneously, vitamin A is difficult to its prescriptionization with topical application.
Therefore, in order to lose activity under the UV-light that solves vitamin A and skin to be had problems such as pungency, people make it become more stable the ester derivative that vitamin A changes into vitamin A.At present, the esterification of vitamin A is mainly chemical method.But the degraded of vitamin A can cause the esterification productive rate very low usually in the chemical method.And reaction can be accompanied by final product and generate a large amount of unwanted other products in the chemical method, as salt etc.
Because the ester derivative of vitamin A more is used for fields such as makeup, medicine and nutritious prod, therefore, to compare with chemical method, the enzyme process esterification of vitamin A has unique advantage as a kind of " green synthesis method ".Wherein, lytic enzyme is because can highly-solid selectively ground catalysis organic acid and alcohol, thereby has been subjected to more concern.At present, the catalysis of these lytic enzymes be widely used in the chemo-selective acidylate of synthetic, sugared stereoselectivity acidylate, amino-sugar derivatives of spices and fatty acid ester and lactone, peptide and chiral drug synthetic in.But present enzyme process esterification need be a carrier with the organic solvent still, can produce a large amount of organic liquid wastes in industrial production, and increases cost.
Summary of the invention
Technical problem to be solved by this invention is: the synthetic method that a kind of soya-bean oil monoester derivates of the vitamin A that can not produce organic liquid waste, economy and environmental protection will be provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the synthetic method of the soya-bean oil monoester derivates of vitamin A, and its structural formula is:
R is a lipid acid in the following formula; Be characterized in: comprise the steps:
(1) under 4-60 ℃, be that the three-necked bottle of 8～12% vitamin A solution is wrapped lucifuge with masking foil with concentration is housed;
(2) soybean oil is added in the three-necked bottle, and soybean oil: the weight ratio of vitamin A is 0.8～1: 1, and the 50-400rpm electric mixer stirs;
(3) ratio according to 1 gram enzyme/1 milliliter soybean oil～1 gram enzyme/32 milliliter soybean oil adds to lipase in the soybean oil;
(4) constant temperature stirring reaction is until obtaining required product;
Above-mentioned synthetic route is expressed as follows with reaction equation:
Following formula R
1, R
2, R
3Be respectively the aliphatic carbon chain that contains 14 carbon to 24 carbon.
Above-mentioned lipase is selected from candida antarctica (Candida Antartica) esterase B, onion bulkholderia cepasea lipase (Burkholderia cepacia Lipase), dredges the thermophilic hyphomycete lipase of cotton shape (Thermomyces lanuginosus Lipase), subtilisin crosslinked enzyme crystal (Cross-LinkingEnzyme Crystal, a kind of in CLECs).
When above-mentioned constant temperature stirring reaction, add the water that accounts for reaction solution volume 0～2%; The preferred water that accounts for reaction solution volume 1% that adds.Add a certain proportion of water to system, can improve the activity of enzyme, but the transformation efficiency of reaction is not had too much influence;
In the process of above-mentioned constant temperature stirring reaction, but also timing sampling uses high performance liquid chromatography (HPLC) method to measure the ratio of product ester and raw material vitamin A, so that the process of monitoring reaction.
After reaction stops, system is centrifugal, enzyme can be reclaimed and use.
Above-mentioned HPLC condition: chromatographic column is
OD (0.46 * 25 centimetre of column, Daicel); Moving phase is hexane/isopropyl alcohol/trifluoroacetic acid (90/10/0.1); Flow velocity is 1 ml/min, and the ultraviolet detection wavelength is 320 nanometers.The retention time of vitamin A monoesters is 3.61 minutes, and the retention time of vitamin A is (to can't see the peak of soybean oil under the lower concentration in 5.28 minutes; Improve concentration, its retention time is 4.05 minutes)
The invention has the beneficial effects as follows: be catalyzer carries out vitamin A by transesterification reaction enzyme process mono-esterification with lipase among the present invention, soybean oil also had been a reaction solvent for reactant simultaneously both in the system, reduced the generation of organic liquid waste, both economy and environmental protection, the reaction yield height, catalyzer is recyclable.
Embodiment
The invention will be further described below by specific embodiment, but do not limit the present invention in any way.
Embodiment 1:
Under 50 ℃ of water-baths, 500 milliliters of three-necked bottles that 10% vitamin A solution is housed are wrapped lucifuge with masking foil; Add 400 milliliters of soybean oil to above-mentioned three-necked bottle, electric mixer stirs, and stirring velocity is 300rpm.25 gram onion bulkholderia cepasea lipase (Burkholderia cepacia Lipase) are added in the soybean oil, and constant temperature stirring reaction, timing sampling are measured the ratio of product ester and raw material vitamin A with HPLC.After 2 hours, after transformation efficiency was 83%, 10 hour, after transformation efficiency rose to 92%, 24 hour, transformation efficiency did not almost change, and is 93%.Stopped reaction, system is centrifugal, enzyme is reclaimed use.
Embodiment 2:
Under 50 ℃ of water-baths, 500 milliliters of three-necked bottles that 10% vitamin A solution is housed are wrapped lucifuge with masking foil; Add 400 milliliters of soybean oil to above-mentioned three-necked bottle, electric mixer stirs, and stirring velocity is 300rpm.20 grams are dredged the thermophilic hyphomycete lipase of cotton shape (Thermomyces lanuginosus Lipase) add in the soybean oil, constant temperature stirring reaction, timing sampling are measured the ratio of product ester and raw material vitamin A with HPLC.After 3 hours, after transformation efficiency was 56.3%, 21 hour, transformation efficiency rose to 85.3%.Stopped reaction, system is centrifugal, enzyme is reclaimed use.
Embodiment 3:
Under the room temperature, 500 milliliters of three-necked bottles that 10% vitamin A solution is housed are wrapped lucifuge with masking foil; Add 400 milliliters of soybean oil to above-mentioned three-necked bottle, electric mixer stirs, and stirring velocity is 300rpm.20 gram onion bulkholderia cepasea lipase (Burkholderia cepacia Lipase) are added in the soybean oil, and add 1 ml water, constant temperature stirring reaction, timing sampling are measured the ratio of product ester and raw material vitamin A with HPLC.After 3 hours, after transformation efficiency was 76.0%, 24 hour, transformation efficiency rose to 81.7%.Stopped reaction, system is centrifugal, enzyme is reclaimed use.
Embodiment 4:
Under the room temperature, 500 milliliters of three-necked bottles that 10% vitamin A solution is housed are wrapped lucifuge with masking foil; Add 400 milliliters of soybean oil to above-mentioned three-necked bottle, electric mixer stirs, and stirring velocity is 300rpm.20 grams are dredged the thermophilic hyphomycete lipase of cotton shape (Thermomyces lanuginosus Lipase) add in the soybean oil, and add 4 ml waters, constant temperature stirring reaction, timing sampling are measured the ratio of product ester and raw material vitamin A with HPLC.After 3 hours, after transformation efficiency was 86.0%, 24 hour, transformation efficiency rose to 90.5%.Stopped reaction, system is centrifugal, enzyme is reclaimed use.
Embodiment 5:
Under the room temperature, 1000 milliliters of three-necked bottles that 10% vitamin A solution is housed are wrapped lucifuge with masking foil; Add 400 milliliters of soybean oil to above-mentioned three-necked bottle, electric mixer stirs, and stirring velocity is 200rpm.400 gram onion bulkholderia cepasea lipase (Burkholderia cepacia Lipase) are added in the soybean oil, and constant temperature stirring reaction, timing sampling are measured the ratio of product ester and raw material vitamin A with HPLC.After 1 hour, after transformation efficiency was 14.2%, 3 hour, after transformation efficiency rose to 68.9%, 24 hour, transformation efficiency rose to 94.9%.Stopped reaction, system is centrifugal, enzyme is reclaimed use.
Embodiment 6:
Under 50 ℃ of water-baths, 1000 milliliters of three-necked bottles that 10% vitamin A solution is housed are wrapped lucifuge with masking foil; Add 400 milliliters of soybean oil to above-mentioned three-necked bottle, electric mixer stirs, and stirring velocity is 200rpm.400 grams are dredged the thermophilic hyphomycete lipase of cotton shape (Thermomyces lanuginosus Lipase) add in the soybean oil, constant temperature stirring reaction, timing sampling are measured the ratio of product ester and raw material vitamin A with HPLC.After 24 hours, transformation efficiency rises to 94.8%.Stopped reaction, system is centrifugal, enzyme is reclaimed for the first time.For the second time repeat above-mentioned reaction, after 24 hours, transformation efficiency is 93.3%.Stopped reaction, system is centrifugal, enzyme is reclaimed for the second time.Repeat above-mentioned reaction for the third time, after 24 hours, transformation efficiency is 90.3%.Stopped reaction, system is centrifugal, enzyme is reclaimed for the third time.Repeat above-mentioned reaction the 4th time, after 24 hours, transformation efficiency is 92.1%.Stopped reaction, system is centrifugal, enzyme is reclaimed for the 4th time.Repeat above-mentioned reaction the 5th time, after 24 hours, transformation efficiency is 96.2%.
Claims (5)
1, the synthetic method of the soya-bean oil monoester derivates of vitamin A, its structural formula is:
R is a lipid acid in the following formula; It is characterized in that: comprise the steps:
(1) under 4-60 ℃, be that the three-necked bottle of 8～12% vitamin A solution is wrapped lucifuge with masking foil with concentration is housed;
(2) soybean oil is added in the three-necked bottle, and soybean oil: the weight ratio of vitamin A is 0.8～1: 1, and the 50-400rpm electric mixer stirs.
(3) ratio according to 1 gram enzyme/1 milliliter soybean oil～1 gram enzyme/32 milliliter soybean oil adds to lipase in the soybean oil;
(4) constant temperature stirring reaction is until obtaining required product.
Above-mentioned synthetic route is expressed as follows with reaction equation:
Following formula R
1, R
2, R
3Be respectively the aliphatic carbon chain that contains 14 carbon to 24 carbon.
2, synthetic method according to claim 1, it is characterized in that: described lipase is selected from candida antarctica (Candida Antartica) esterase B, onion bulkholderia cepasea lipase (Burkholderiacepacia Lipase), dredges the thermophilic hyphomycete lipase of cotton shape (Thermomyces lanuginosus Lipase), subtilisin crosslinked enzyme crystal (Cross-Linking Enzyme Crystal, a kind of in CLECs).
3, synthetic method according to claim 1 and 2 is characterized in that: add the water that accounts for reaction solution volume 0～2% when the constant temperature stirring reaction.
4, synthetic method according to claim 3 is characterized in that: add the water that accounts for reaction solution volume 1% when the constant temperature stirring reaction.
5, synthetic method according to claim 1 and 2 is characterized in that: in the process of constant temperature stirring reaction, timing sampling is with the ratio of high performance liquid chromatography (HPLC) method mensuration product ester and raw material vitamin A, so that the process of monitoring reaction.
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| CNA2008101238632A CN101285088A (en) | 2008-06-11 | 2008-06-11 | Synthetic method of soya-bean oil monoester derivates of vitamin A |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103110672A (en) * | 2012-09-26 | 2013-05-22 | 王德俭 | Dark herba portulacae preparation method for treating whelk |
| CN112921064A (en) * | 2019-12-06 | 2021-06-08 | 浙江医药股份有限公司昌海生物分公司 | Method for synthesizing vitamin A palmitate under catalysis of immobilized enzyme |
-
2008
- 2008-06-11 CN CNA2008101238632A patent/CN101285088A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103110672A (en) * | 2012-09-26 | 2013-05-22 | 王德俭 | Dark herba portulacae preparation method for treating whelk |
| CN112921064A (en) * | 2019-12-06 | 2021-06-08 | 浙江医药股份有限公司昌海生物分公司 | Method for synthesizing vitamin A palmitate under catalysis of immobilized enzyme |
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Open date: 20081015 |