CN114989125A - Preparation method of low-color-number vitamin E acetate - Google Patents
Preparation method of low-color-number vitamin E acetate Download PDFInfo
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- CN114989125A CN114989125A CN202210595759.3A CN202210595759A CN114989125A CN 114989125 A CN114989125 A CN 114989125A CN 202210595759 A CN202210595759 A CN 202210595759A CN 114989125 A CN114989125 A CN 114989125A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention provides a preparation method of low-color-number vitamin E acetate. The method comprises the step of reacting 2,3, 5-trimethylhydroquinone diacetate with isophytol in the presence of a catalyst, an auxiliary agent and a solvent to prepare the low-color-number vitamin E acetate. The vitamin E acetate prepared by the process has the characteristics of low product color number and convenience for downstream application.
Description
Technical Field
The invention belongs to the field of fine chemical synthesis, and particularly relates to a preparation method of vitamin E acetate.
Background
Vitamin e (vitamin e) is a fat-soluble vitamin whose hydrolysate is tocopherol, one of the most important antioxidants. The tocopherol can promote the secretion of sex hormone, so that the vitality and the quantity of sperms of the male are increased; increase female estrogen concentration, improve fertility, prevent abortion, and can be used for preventing and treating male infertility, burn, cold injury, capillary hemorrhage, climacteric syndrome, and skin care. The vitamin E acetate has wide application prospect and market value in the fields of medicine, food, cosmetics, feed and the like.
Chinese patent CN109651255B discloses an imidazole ionic liquid and its preparation and application in vitamin E synthesis, the method needs to carry out catalyst preparation, 2,3, 5-trimethylhydroquinone diacetate and isophytol react to generate partial products, and then excessive acetic anhydride needs to be added to carry out esterification reaction to obtain the final product, and more equipment is needed in the industrial amplification process, which leads to the increase of equipment cost. The product prepared by the method has the problems of high product color number and influence on downstream application.
European patent EP1583753(A1) provides a process for the preparation of alpha-tocopheryl acetate by reaction of 2,3, 6-trimethylhydroquinone-1-acetate with a phytol or isophytol or (iso) phytol derivative in the presence of a catalyst of the formula Mn + (Rl SO3-) n in an aprotic organic solvent. However, the reaction product is a mixture containing vitamin E acetate, vitamin E and the like, a vitamin E acetate product without vitamin E can be obtained only when one raw material is excessive, and the mixture of the vitamin E and the vitamin E acetate can be subjected to esterification reaction to obtain the vitamin acetate with higher concentration.
European patent EP603695 provides the synthesis of vitamin E by condensation of trimethylhydroquinone and isophytol in a liquid or supercritical carbon dioxide system using acidic catalysts hydrochloric acid, zinc chloride and ion exchangers as catalysts. The operation process of the process is complex, the catalyst is difficult to recycle, the problems of serious equipment corrosion and troublesome waste liquid treatment exist, and after the experiment is carried out according to the method, more isophytol is deteriorated to generate heavy components, so that the color number of the product is higher, and the method is not an ideal downstream application scheme.
In conclusion, the existing method for preparing the vitamin E acetate has the problems of complex process route, strict process requirements, low utilization rate of raw materials, high product color number and the like, and the final product vitamin E acetate can be obtained only by multi-step reactions. Therefore, a new method for preparing vitamin E acetate needs to be found to solve the above technical problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of low-color-number vitamin E acetate, which is prepared by reacting 2,3, 5-trimethylhydroquinone diacetate with isophytol.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of low-color-number vitamin E acetate, which comprises the step of reacting 2,3, 5-trimethylhydroquinone diacetate with isophytol in the presence of a catalyst, an auxiliary agent and a solvent to prepare the low-color-number vitamin E acetate.
Wherein, the structures of 2,3, 5-trimethylhydroquinone diacetate (TMHQ-DA) and Isophytol (IPL) are respectively shown in formulas (1) and (2):
the structure of the target product vitamin E acetate is shown as the formula (3):
in which Ac represents CH 3 CO-。
In the present invention, the 2,3, 5-trimethylhydroquinone diacetate (TMHQ-DA) is a raw material known in the art, and the preparation method thereof is not limited, and the raw material can be prepared according to the method disclosed in the prior art, for example, the method disclosed in patent CN 104387269B.
In the present invention, the catalyst is a combination of a metal halide and a protonic acid.
Preferably, the metal halide is selected from any one of or a combination of at least two of alkaline earth metal halides, transition metal halides, and group IIIA-VA metal halides; more preferably any one or a combination of at least two of beryllium chloride, magnesium chloride, calcium chloride, titanium chloride, vanadium chloride, barium chloride, ferrous chloride, ferric chloride, cuprous chloride, cupric chloride, manganese chloride, zinc chloride, silver chloride, aluminum chloride, sodium bromide, manganese bromide, barium bromide, cupric bromide, magnesium bromide, zinc bromide, aluminum bromide, thallium bromide, mercuric bromide, silver iodide, zinc iodide, and ferrous iodide, and further preferably any one or a combination of at least two of aluminum chloride, ferrous chloride, ferric chloride, cupric chloride, zinc chloride, aluminum bromide, ferric bromide, zinc iodide, and ferrous iodide.
Preferably, the protonic acid is selected from the group consisting of protonic acids comprising group VIA, group VIIA, group VIIB elements, more preferably any one or a combination of at least two of chlorosulfonic acid, sulfonic acid, selenic acid, hydrochloric acid, hydrobromic acid, iodic acid, hydrogen iodide, pyrophosphoric acid, sulfuric acid, tungstic acid.
In some preferred embodiments, the metal halide is present in the catalyst in an amount of 0.05 to 100%, for example 0.1%, 0.5%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 45%, preferably 1 to 50%, more preferably 2 to 40% by mass of 2,3, 5-trimethylhydroquinone diacetate.
In some preferred embodiments, the protonic acid is used in the catalyst in an amount of 0.01 to 60% by mass, for example 0.5%, 5%, 10%, 15%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, preferably 0.1 to 30% by mass, based on the mass of 2,3, 5-trimethylhydroquinone diacetate.
In the present invention, the auxiliary is selected from aniline compounds, preferably, m-chlorodiphenylamine, (4-chlorophenyl) -phenylamine, p-hydroxydiphenylamine, 2, 6-dichlorodiphenylamine, 4-chloro-N, 2-dihydroxyaniline, N-diphenylacetamide, and the like, either singly or in combination of at least two kinds thereof.
In some preferred embodiments, the amount of auxiliary agent is 0.001 to 10%, for example 0.005%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, preferably 0.01 to 8% by mass of 2,3, 5-trimethylhydroquinone diacetate.
In experimental research on the preparation of vitamin E acetate by reacting 2,3, 5-trimethylhydroquinone diacetate with isophytol, the invention discovers that the isophytol serving as a raw material is easy to deteriorate in a reaction system to generate heavy component impurities, the heavy component impurities have obvious influence on the color of a vitamin E acetate product, and the addition of a certain amount of aniline compounds serving as an auxiliary agent can inhibit the deterioration of the isophytol, so that the generation amount of color-developing impurities generated by the deterioration of the isophytol is reduced, and the low-color-number vitamin E acetate is obtained.
In the present invention, in the preparation of vitamin E acetate, the reaction of 2,3, 5-trimethylhydroquinone diacetate with isophytol is carried out in the presence of a solvent selected from any one or a combination of at least two of halogenated alkanes, aliphatic alkanes, alicyclic alkanes, carboxylic acids, carboxylic anhydrides, aliphatic alcohols, halogenated benzenes, preferably any one or a combination of at least two of dichloromethane, carbon tetrachloride, 1, 2-dichloroethane, chlorobenzene, n-hexane, cyclohexane, n-heptane, n-octane, petroleum ether (30-60 ℃ C.), petroleum ether (60-90 ℃ C.), petroleum ether (90-120 ℃ C.), acetic acid, ethyl acetate, acetic anhydride, methanol, ethanol, isopropanol, and the like.
In some preferred embodiments, the amount of the solvent is 0.1 to 30 times, for example 0.2 times, 0.5 times, 1 time, 1.5 times, 2 times, 3 times, 5 times, 10 times, 15 times, preferably 0.3 to 20 times the mass of 2,3, 5-trimethylhydroquinone diacetate.
In some embodiments of the invention, the molar ratio of 2,3, 5-trimethylhydroquinone diacetate to isophytol is 1: (0.8-2), for example, 1: 1.0, 1: 1.05, 1: 1.2, 1: 1.5, preferably 1 (0.9-1.1).
In some embodiments of the invention, the reaction of 2,3, 5-trimethylhydroquinone diacetate with isophytol is carried out at a temperature of from 0 to 140 deg.C, for example 20 deg.C, 40 deg.C, 60 deg.C, 80 deg.C, 100 deg.C, 110 deg.C, 130 deg.C, preferably 30 to 120 deg.C.
In the method of the invention, when preparing the vitamin E acetate, the charging sequence of the two raw materials, namely 2,3, 5-trimethylhydroquinone diacetate and isophytol, is that one raw material is firstly added into a reaction system, and then the other raw material is charged in a continuous charging mode (preferably a dropwise mode); for example, 2,3, 5-trimethylhydroquinone diacetate is firstly put into a reaction system, and isophytol is then continuously added into the reaction system, wherein the reaction process comprises a feeding process and a post-feeding heat preservation process, the feeding time is 0.05-24h, such as 0.1h, 0.5h, 1h, 5h, 10h, 15h, 20h, preferably 1-15h, the post-feeding heat preservation time is 0-10h, such as 0.1h, 0.5h, 1h, 5h, 8h, preferably 0.1-6h, the feeding time and the post-feeding heat preservation time are both contained in the reaction time, and the system temperature is controlled to be the same as the reaction temperature in the processes of dropwise adding and heat preservation after dropwise adding.
In the method, after the reaction is finished, the post-treatment processes of separation, desolventization, washing, removal of recombinant components and the like are included, and the method is conventional operation in the field and has no special requirement.
According to the method, the conversion rate of the TMHQ-DA raw material can reach more than 99%, the selectivity of the product vitamin E acetate can reach more than 98%, and the selectivity of heavy component impurities generated by metamorphic allophytol is lower than 0.5%.
The color number of the product prepared by the method is lower than 50 Hzaen.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
according to the method for preparing the vitamin E acetate by reacting the 2,3, 5-trimethylhydroquinone diacetate with the isophytol, the aniline substances are introduced as the auxiliary agents, so that the selectivity and the yield can be improved, the deterioration of the isophytol can be inhibited, and the color development impurities generated by the deterioration of the isophytol are reduced.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The source information of the main raw materials used in the examples and comparative examples of the present invention is as follows, and the other raw materials of the reagents are all common commercial products unless otherwise specified:
IPL: 96% of Aladdin;
BN (boron nitride): 99.9 percent of Allatin;
NiCl 2 (nickel chloride): new chemical company, dennan ang;
(4-chlorophenyl) -phenylamine: carbofuran;
m-chloro diphenylamine: carbofuran;
2, 6-dichlorodiphenylamine: carbofuran;
4-chloro-N, 2-dihydroxyaniline: carbofuran;
n, N-diphenylacetamide: carbofuran;
p-hydroxy diphenylamine: carbofuran;
2,6, 6-trimethylcyclohex-2-ene-1, 4-dione: wuhan remote co-creation, 98%;
TMHQ-DA: prepared according to the method of patent CN104387269B example 1.
The product selectivity and conversion referred to in the examples of the invention were analyzed by gas chromatography under the following conditions:
the gas chromatograph is Agilent 7820A, a capillary column (DB-5, 30m × 0.25mm × 0.25 μm), the temperature is programmed in the second step, the initial temperature is 100 ℃, and the temperature is raised to 130 ℃ at the speed of 5 ℃/min after the temperature is maintained for 2 minutes; then the temperature was increased to 280 ℃ at a rate of 15 ℃/min and held for 22 minutes. Carrier gas high purity N 2 The split ratio is 20: 1. the sample introduction temperature is 290 ℃, the detector is FID, the detector temperature is 300 ℃, and the sample introduction amount is 0.2 mu L.
Examples 1 to 8
Preparing low-color-number vitamin E acetate, comprising the following steps:
adding TMHQ-DA, a solvent, a metal halide, protonic acid and an aniline compound into a 500mL three-neck flask, stirring, heating until the solid is completely dissolved, then dropwise adding IPL, continuing to perform heat preservation reaction after the dropwise adding is finished, and sampling and analyzing the conversion rate of the raw material TMHQ-DA, the selectivity of the product vitamin E acetate and the selectivity of heavy component impurities generated by metamorphism of isophytol after the reaction is finished.
Stopping stirring, standing for 30min, separating the reaction solution into two layers, the upper layer is a vitamin E acetate product phase, the lower layer is a catalyst phase and a solvent phase, desolventizing, washing and removing weight of the obtained product phase to obtain a vitamin E acetate product, and testing the purity and color number of the separated product to be 98.7%.
The kinds and ratios of the raw materials used in examples 1 to 8 are specifically shown in Table 1, and the reaction conditions and the results of the analyses are shown in Table 2.
TABLE 1 examples 1-8 raw material types and ratios
Table 2 examples 1-8 reaction conditions and analysis of results
Comparative example 1
Referring to the method of example 1, except that the auxiliary agent 2, 6-dichlorodiphenylamine was not added, the other operations and parameters were the same as those of example 1, and after the reaction was completed, the conversion rate of the raw material TMHQ-DA was 98.1%, the selectivity of the product vitamin E acetate was 84.6%, and the selectivity of the heavy component impurity generated by the degeneration of isophytol was 13.7%.
The reaction solution was treated in the same manner as in example 1 to give a product having a purity of 89.4% and a color number of 820 Hazen.
Comparative example 2
Referring to the method of example 1, except that the auxiliary agent was replaced by benzaldehyde, the other operations and parameters were the same as those of example 1, and after the reaction was completed, the conversion rate of TMHQ-DA as a raw material was 98.4%, the selectivity of vitamin E acetate as a product was 85.9%, and the selectivity of heavy component impurities generated by the deterioration of isophytol was 12.9%.
The reaction solution was treated in the same manner as in example 1 to obtain a product having a purity of 90.2% and a color number of 769 Hazen.
Comparative example 3
Referring to the method of example 1, except that the auxiliary agent is replaced by triethylamine, the other operations and parameters are the same as those of example 1, after the reaction is completed, the conversion rate of the raw material TMHQ-DA is 98.8%, the selectivity of the product vitamin E acetate is 88.1%, and the selectivity of heavy component impurities generated by the deterioration of isophytol is 9.4%.
The reaction mixture was treated in the same manner as in example 1 to give a product having a purity of 91.1% and a color number of 708 Hazen.
Claims (10)
1. The preparation method of the low-color-number vitamin E acetate is characterized in that the low-color-number vitamin E acetate is prepared by reacting 2,3, 5-trimethylhydroquinone diacetate with isophytol in the presence of a catalyst, an auxiliary agent and a solvent.
2. The method of claim 1, wherein the catalyst is a combination of a metal halide and a protic acid.
3. The method of claim 2, wherein the metal halide is selected from any one of or a combination of at least two of an alkaline earth metal halide, a transition metal halide, and a group IIIA-VA metal halide; more preferably any one or a combination of at least two of beryllium chloride, magnesium chloride, calcium chloride, titanium chloride, vanadium chloride, barium chloride, ferrous chloride, ferric chloride, cuprous chloride, cupric chloride, manganese chloride, zinc chloride, silver chloride, aluminum chloride, sodium bromide, manganese bromide, barium bromide, cupric bromide, magnesium bromide, zinc bromide, aluminum bromide, thallium bromide, mercuric bromide, silver iodide, zinc iodide, and ferrous iodide, and further preferably any one or a combination of at least two of aluminum chloride, ferrous chloride, ferric chloride, copper chloride, zinc chloride, aluminum bromide, ferric bromide, zinc iodide, and ferrous iodide;
the protonic acid is selected from protonic acids containing elements of groups VIA, VIIA and VIIB, and is preferably one or a combination of at least two of chlorosulfonic acid, sulfonic acid, selenic acid, hydrochloric acid, hydrobromic acid, iodic acid, hydrogen iodide, pyrophosphoric acid, sulfuric acid and tungstic acid.
4. A process according to claim 2 or 3, characterized in that the metal halide is used in an amount of 0.05 to 100%, preferably 1 to 50%, more preferably 2 to 40% by mass of 2,3, 5-trimethylhydroquinone diacetate;
the amount of the protonic acid is 0.01-60%, preferably 0.1-30% of the mass of the 2,3, 5-trimethylhydroquinone diacetate.
5. A method according to any one of claims 1 to 4, characterized in that the auxiliary agent is selected from any one of or a combination of at least two of aniline compounds, preferably m-chlorodiphenylamine, (4-chlorophenyl) -phenylamine, p-hydroxydiphenylamine, 2, 6-dichlorodiphenylamine, 4-chloro-N, 2-dihydroxyaniline, N-diphenylacetamide.
6. A process according to any one of claims 1 to 5, characterized in that the auxiliary agent is used in an amount of 0.001 to 10%, preferably 0.01 to 8% by mass of 2,3, 5-trimethylhydroquinone diacetate.
7. The process according to any one of claims 1 to 6, wherein the reaction is carried out in the presence of a solvent selected from any one or a combination of at least two of halogenated alkanes, aliphatic alkanes, alicyclic alkanes, carboxylic acids, carboxylic anhydrides, aliphatic alcohols, halogenated benzenes, preferably any one or a combination of at least two of dichloromethane, carbon tetrachloride, 1, 2-dichloroethane, chlorobenzene, n-hexane, cyclohexane, n-heptane, n-octane, petroleum ether, acetic acid, ethyl acetate, acetic anhydride, methanol, ethanol, isopropanol;
the dosage of the solvent is 0.1 to 30 times, preferably 0.3 to 20 times of the mass of the 2,3, 5-trimethylhydroquinone diacetate.
8. The process according to any one of claims 1 to 7, wherein the molar ratio of 2,3, 5-trimethylhydroquinone diacetate to isophytol is 1: (0.8-2), preferably 1 (0.9-1.1);
the reaction temperature is 0-140 ℃, preferably 30-120 ℃.
9. The process according to any one of claims 1 to 8, wherein the starting materials 2,3, 5-trimethylhydroquinone diacetate and isophytol are fed in the order of adding one of the starting materials to the reaction system and then feeding the other starting material in a continuous feed manner, wherein the reaction process comprises a feed process and a post-feed incubation process, wherein the feed time is 0.05 to 24 hours, preferably 1 to 15 hours, and the post-feed incubation time is 0 to 10 hours, preferably 0.1 to 6 hours.
10. The process of any one of claims 1-9, wherein the vitamin E acetate product produced has a color number of less than 50 Hzaen.
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| CN115745938A (en) * | 2022-11-15 | 2023-03-07 | 万华化学集团股份有限公司 | Method for continuously preparing vitamin E acetate |
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| CN105801551A (en) * | 2014-12-29 | 2016-07-27 | 浙江新和成药业有限公司 | Clean production method of vitamin E acetate |
| CN106565659A (en) * | 2016-11-01 | 2017-04-19 | 万华化学集团股份有限公司 | Method of preparing vitamin E acetate |
| CN109705082A (en) * | 2018-12-19 | 2019-05-03 | 万华化学集团股份有限公司 | A method of preparing vitamin e acetate |
| CN111646968A (en) * | 2020-05-28 | 2020-09-11 | 万华化学集团股份有限公司 | Method for preparing vitamin E |
| CN112920154A (en) * | 2021-01-29 | 2021-06-08 | 蚌埠学院 | Method for synthesizing vitamin E acetate by catalyzing sodium bisulfate doped with polyaniline |
| CN113083339A (en) * | 2021-04-15 | 2021-07-09 | 万华化学(四川)有限公司 | Catalyst for preparing vitamin E and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115745938A (en) * | 2022-11-15 | 2023-03-07 | 万华化学集团股份有限公司 | Method for continuously preparing vitamin E acetate |
| CN115745938B (en) * | 2022-11-15 | 2024-05-03 | 万华化学集团股份有限公司 | Method for continuously preparing vitamin E acetate |
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