CN105418574A - dl-alpha tocopherol acetate preparation method - Google Patents
dl-alpha tocopherol acetate preparation method Download PDFInfo
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- CN105418574A CN105418574A CN201410425681.6A CN201410425681A CN105418574A CN 105418574 A CN105418574 A CN 105418574A CN 201410425681 A CN201410425681 A CN 201410425681A CN 105418574 A CN105418574 A CN 105418574A
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Abstract
The present invention relates to a dl-alpha tocopherol acetate preparation method, wherein trimethyl hydroquinone diethyl ester or trimethyl hydroquinone-4-ethyl ester is adopted as a raw material, Bronsted acid and Lewis acid are adopted as catalysts, the raw material and phytol or isophytol or a phytol derivative are directly subjected to a condensation reaction in an ester solvent to obtain the product dl-alpha tocopherol acetate or an intermediate dl-alpha tocopherol, wherein the intermediate dl-alpha tocopherol is subjected to further esterification to obtain the product dl-alpha tocopherol acetate. According to the present invention, the process route is simple, the production cost is reduced, the quality of the obtained product is good, the yield is high, and the method is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to and use Trimethylhydroquinone diethyl ester or Trimethylhydroquinone-1-ethyl ester to prepare the method for dl-alpha-tocopherol acetic ester for raw material condensation reaction, wherein Trimethylhydroquinone diethyl ester is that raw material condensation reaction directly obtains dl-alpha-tocopherol acetic ester product, Trimethylhydroquinone-1-ethyl ester is that raw material condensation reaction obtains dl-alpha-tocopherol, obtains dl-alpha-tocopherol acetic ester product through further esterification.
Background technology
VITAMIN is as maintaining the necessary type organic of human life activity, also be the important active substances keeping HUMAN HEALTH, play an important role in the processes such as growth in humans, metabolism, growth, breeding, wherein vitamin-E is a kind of liposoluble vitamin, be mainly the important composition composition of cytolemma, mainly play oxidation resistant effect.
Vitamin-E mainly has anti-oxidant, anti-ageing, function such as raising immunizing power, antisterility etc.; be mainly used in the treatment of infertile and promotion reproduction clinically in early days; present then more for beautifying and anti-aging, Green Tea Extract oxidation, protection red corpuscle, protection T lymphocyte, improve blood circulation, anticoagulant, treatment involution syndrome and treatment burn frostbite etc., actual product is then mainly used in medicine, food, makeup and fodder additives.
Vitamin-E mainly comprises natural VE (comprising d-alpha-tocopherol and d-alpha-tocopherol acetic ester etc.) and synthesising complex E (comprising dl-alpha-tocopherol and dl-alpha-tocopherol acetic ester etc.), wherein natural VE mainly comes from the extraction of vegetables oil, owing to being limited by raw material sources, the output of natural VE and range of application are not very large, and main synthesising complex E comes from the synthesis technique of full chemical industry substantially, be of wide application, output and demand are all very large.
Existing synthesising complex E synthesis technique major part is all adopt Trimethylhydroquinone
for raw material, be obtained by reacting dl-alpha-tocopherol by carrying out F-C with isophytol or phytol or phytol derivative etc. under all kinds of catalyst action, then obtain dl-alpha-tocopherol acetic ester through carrying out esterification with acetic acid or aceticanhydride.
Reaction mechanism is as follows:
R
1group comprises hydroxyl, halogen, acetoxyl group, benzoyloxy, mesyloxy, ethanesulfonyloxy group, phenylsulfonyloxy or tosyloxy.
There is following defect in these reactions: the 1) synthesis of raw material Trimethylhydroquinone comparatively Trimethylhydroquinone monoesters or Trimethylhydroquinone diester complexity, and cost is higher; 2) raw material Trimethylhydroquinone is unstable, easily oxidized, not easily stores; 3) there is certain toxicity in raw material Trimethylhydroquinone, exist with the pressed powder state of lightweight, easily in atmosphere floating or be adsorbed onto on human body, larger pungency can be produced to human body skin, respiratory tract etc., thus certain environmental influence and occupational illness risk are brought to actual production; 4) the dl-alpha-tocopherol be obtained by reacting is easily oxidized, generally will carry out esterification and obtain dl-alpha-tocopherol acetic ester, and technics comparing is complicated, and esterification must consume certain acetic acid or aceticanhydride and energy etc. simultaneously.
Also partial synthesis process choice Trimethylhydroquinone carboxylate (comprising Trimethylhydroquinone monoesters or Trimethylhydroquinone diester) is had as raw material, although above-mentioned defect can be overcome to a certain extent, but also there is certain drawback, wherein Trimethylhydroquinone-4-ester (
r
4group is the group such as hydrogen or methyl) due to the factor of limited reactions such as carrying out that F-C reaction (reaction site is positioned at 1, No. 6 position on phenyl ring) does not have steric hindrance and group active, so reaction is carried out than being easier to, also dl-alpha-tocopherol acetic ester can directly be obtained, but because material choice has certain limitation, Trimethylhydroquinone-4-ester can only be selected, and Trimethylhydroquinone-4-ester is mainly derived from the reactions such as the enzymolysis of Trimethylhydroquinone diester, this type of reaction is comparatively complicated, and cost is also higher.
Trimethylhydroquinone diester (
r
5, R
6group is the group such as hydrogen or methyl) or Trimethylhydroquinone-1-ester (
r
7group is the group such as hydrogen or methyl) then more immature as the synthesis technique of raw material, because on phenyl ring, No. 1 position is esterified in Trimethylhydroquinone diester or the Trimethylhydroquinone-1-ester structure of matter, participate in F-C reaction and there is the limiting factor such as steric hindrance and group activity, raw material reaction activity is less, disclosed in major part document, technological reaction degree is less, reaction yield is lower, and the quality product obtained is poor.
Also some processes is had to select first to be hydrolyzed by Trimethylhydroquinone carboxylate etc. to be obtained by reacting Trimethylhydroquinone, and then be obtained by reacting synthesising complex E product with isophytol or phytol etc., cause technics comparing complicated like this, cost increases greatly, in process control procedure, intermediate Trimethylhydroquinone is easily oxidized, the product quality finally obtained is poor, the problems such as the many environmental pollutions simultaneously also brought.
Have part document to disclose at present Trimethylhydroquinone monoesters or Trimethylhydroquinone diester carry out synthesizing dl-alpha-tocopherol acetic ester technique as initial feed, as
Mention in DE10011402 patent and directly use Trimethylhydroquinone diethyl ester and isophytol to react, use polar solvent (as acetic acid) as reaction medium, the method mainly utilizes polar solvent acetic acid catalyzer thus is convenient to later stage recovery, and solvent acetic acid etc. is not easily decomposed, loss is less, but Trimethylhydroquinone diethyl ester is not easily sloughed second carboxyl thus is hindered and forms product dl-alpha-tocopherol or dl-alpha-tocopherol acetic ester with isophytol cyclization in acetic acid polar solvent, thus cause process recovery ratio lower, simultaneously because acetic acid in industry and water are difficult to be separated, can constantly accumulate so apply mechanically water-content in catalyzer, later stage catalyst failure is caused to react by catalyzing and condensing.
The statement of EP02025989 patent adopts Trimethylhydroquinone-4-ethyl ester and isophytol or phytol to react, solvent is aprotic organic solvent, catalyzer only adopts sulphonic acids catalyzer or basic catalyst, finally obtain dl-alpha-tocopherol acetic ester, this invented technology is restricted to Trimethylhydroquinone-4-ethyl ester to raw material, has certain limitation, simultaneously in sulphonic acids catalyzer or basic catalyst, condensation reaction is also more difficult, causes product yield lower, yield 10.2 ~ 81.9%.
Patent EP03000493/EP03024288 adopts special catalyst catalysis Trimethylhydroquinone-4-ethyl ester and phytol, isophytol or (different) phytol derivative to be obtained by reacting dl-alpha-tocopherol acetic ester, wherein catalyzer adopts containing precious metal or rare earth compound, raw material is also restricted to Trimethylhydroquinone-4-ethyl ester, there is limitation in limitation, catalyzer causes process costs higher, and temperature of reaction is higher, technique is slightly complicated.
EP04013713 patent is also adopt Trimethylhydroquinone-4-ester (comprising the ester such as ethyl ester, propyl ester class) and isophytol, phytol or (different) phytol derivative to react, the salt compound containing rare metal selected by catalyzer, its Raw is restricted to Trimethylhydroquinone-4-ester, require that condensation reaction is carried out under a certain pressure, reaction conditions is comparatively complicated, and selecting of catalyzer causes process costs higher.
EP01104141.5 patent then adopts suitable biological esterase that Trimethylhydroquinone diethyl ester is first transformed into Trimethylhydroquinone-4-ethyl ester, then carry out follow-up corresponding F-C reaction condensation after purifying again and obtain dl-alpha-tocopherol acetic ester, wherein suitable biological esterase cost can cause process costs greatly to increase, for ensureing biological esterase activity, enzymolysis and separation process conditions require higher, and operational path is also comparatively complicated.
Chinese patent CN201110198791 adopts one kettle way to carry out Trimethylhydroquinone diethyl ester and isophytol reacts, technique first uses lower aliphatic alcohols to carry out transesterification reaction with Trimethylhydroquinone diethyl ester under acid catalysis and obtains Trimethylhydroquinone, then the acetic acid low-grade fatty acid ester of lower aliphatic alcohols and generation is reclaimed, obtain Trimethylhydroquinone solid, and then carry out follow-up condensation reaction and esterification obtains dl-alpha-tocopherol acetic ester, there is certain defect in the method: reclaims Trimethylhydroquinone in the process of lower aliphatic alcohols and fatty acid ester and be easy to oxidized; It is solid-state for reclaiming Trimethylhydroquinone in the process of lower aliphatic alcohols and ester, is difficult to realize in actual industrial production; Transesterification reaction is difficult to completely, causes the finished product yield lower, quality product variation etc.
Disclosed technical literature all has certain defect above, and wherein partial synthesis technique is comparatively complicated, and cost is higher; it is poor that some processes obtains product quality; yield is lower, and also have the processing condition of some processes higher, large-scale production has certain limitation etc.
Summary of the invention
The invention provides the preparation method of dl-alpha-tocopherol acetic ester, preparation method described in described preparation method with Trimethylhydroquinone diethyl ester (I) or Trimethylhydroquinone-4-ethyl ester (II) for raw material, Bronsted acid and Lewis acid are catalyzer, in esters solvent directly and phytol (III) or isophytol (IV) or phytol derivative (V) carry out condensation reaction and obtain dl-alpha-tocopherol acetic ester or dl-alpha-tocopherol, wherein dl-alpha-tocopherol acetic acid or the further esterification of acetic anhydride obtain dl-alpha-tocopherol acetic ester, wherein: the structural formula of Trimethylhydroquinone diethyl ester (I) or Trimethylhydroquinone-4-ethyl ester (II) is as follows:
The structural formula of isophytol (III) or phytol (IV) or phytol derivative (V) is as follows:
Wherein: R in phytol derivative (V) structural formula
1group comprises hydroxyl, halogen, acetoxyl group, benzoyloxy, mesyloxy, ethanesulfonyloxy group, phenylsulfonyloxy or tosyloxy.Reaction process is as follows:
Preferably, described Bronsted acid is selected from least one in hydrochloric acid, Hydrogen bromide, phosphoric acid, sulfuric acid and tosic acid, and described Lewis acid is selected from least one in aluminum chloride, alchlor, aluminium hydroxide, aluminum oxide, iron trichloride, ferric bromide, hydrogenation iron, ferric oxide, zinc chloride, zinc bromide, zinc hydroxide, hydroxy chlorination zinc and hydroxyl zinc bromide.
Preferably, described esters solvent is low-grade fatty acid ester R
2cOOR
3and/or carbonic ether, wherein, R
2representative has the lower alkyl alkyl of 1 ~ 4 carbon atom, R
3representative has the lower alkyl alkyl of 1 ~ 5 carbon atom.More preferably, described low-grade fatty acid ester R
2cOOR
3be selected from least one in methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert.-butyl acetate, n-amyl acetate, Isoamyl Acetate FCC, sec-amyl acetate, tert.-amyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl isobutyrate, methyl valerate, Ethylisovalerate and PIVALIC ACID CRUDE (25) ethyl ester; Described carbonic ether is selected from least one in methylcarbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl ester, ethylene carbonate, Texacar PC.
Preferably, described Bronsted acid is 0.05 ~ 0.5: 1 with the mole ratio of Trimethylhydroquinone-1-ethyl ester or Trimethylhydroquinone diethyl ester, and described Lewis acid is 0.2 ~ 1.0: 1 with the mole ratio of Trimethylhydroquinone-1-ethyl ester or Trimethylhydroquinone diethyl ester.Preferably, the weight of described esters solvent is 1.5 ~ 6 times of the weight of Trimethylhydroquinone-1-ethyl ester or Trimethylhydroquinone diethyl ester.Preferably, the mole ratio of phytol or isophytol and Trimethylhydroquinone diethyl ester or Trimethylhydroquinone-1-ethyl ester is 0.9 ~ 1.1: 1.
Preferably, the temperature of condensation reaction is 30 ~ 80 DEG C.More preferably, the time of condensation reaction is 2 ~ 8 hours.
Preferably, after condensation reaction completes, catalyzer extracts by use water from reaction solution, can direct recycled in lower batch reaction after concentrated, and the waste water of concentrated generation also can directly as extracting catalyst recycled water after lower batch reaction.
In reaction process process of the present invention, the solvent of reaction system generally decomposes less, less to technogenic influence in certain scope, can apply mechanically by direct circulation, when (main decomposition becomes Carboxylic acid and alcohol) after solvolysis to a certain extent, need to process accordingly, as reached purifying object by simple distillation or rectifying, and then continue recycle.In reaction process process of the present invention, the charging capacity of catalysts and solvents is all less, reaction times is shorter, add a small amount of water after having reacted and catalyst extraction out can directly be obtained product or intermediate, and the catalyzer extracted can obtain applying mechanically catalyzer through the process of simple distillation recycle-water.
Technique of the present invention on the whole technological process is fairly simple, and technology stability is better, and obtain product quality better, yield is higher, and the waste water simultaneously produced, waste gas etc. are less, is applicable to industrial scale and produces.
Accompanying drawing explanation
Fig. 1 is dl-alpha-tocopherol acetic ester vapor detection collection of illustrative plates;
Fig. 2 is dl-alpha-tocopherol acetic ester mass-spectrogram;
Fig. 3 be dl-alpha-tocopherol acetic ester nuclear magnetic resonance map (
13c composes);
Fig. 4 be dl-alpha-tocopherol acetic ester nuclear magnetic resonance map (
1h composes);
Fig. 5 is dl-alpha-tocopherol acetic ester infrared spectra collection of illustrative plates.
Embodiment
Further illustrate the present invention by embodiment below, embodiments of the invention are only for illustration of technical scheme of the present invention, and non-limiting the present invention.
Embodiment 1
In reaction flask, add 1.0 molar part (236.5g) Trimethylhydroquinone diethyl ester, then add solvent ethyl acetate 700g, hydrochloric acid 0.1mol, AlCl
30.2mol, then add isophytol 1.0 molar part (297.0g), feed intake complete, stir, start heating, start reaction under temperature 60 C condition, in 6.0 hours reaction times, reaction completes.
In reaction solution, add 100ml water, stir evenly, leave standstill, branch vibration layer, repeat 2 times, organic layer shows orange red, reclaim under reduced pressure organic layer solvent, obtains product dl-alpha-tocopherol acetic ester 464.5g.
Combining water layer, reclaim under reduced pressure moisture content, obtains applying mechanically catalyzer 36.5g; What above-mentioned organic layer recovery obtained is apply mechanically solvent ethyl acetate 695g.
Detect dl-alpha-tocopherol acetic ester sample, dl-alpha-tocopherol content 0.08%, dl-alpha-tocopherol acetate content 96.51%, obtaining technological experiment yield is 94.94% (detect collection of illustrative plates and see accompanying drawing).
Solvent ethyl acetate content 99.4% is applied mechanically in detection, and solvolysis is little, yield 98.6%; Hydrochloric 8.0% is applied mechanically in detection, yield 80%, AlCl
3content 69.5%, yield 95%, catalyst recovery effect is better.
Comparing embodiment 2
In reaction flask, add 1.0 molar part (236.5g) Trimethylhydroquinone diethyl ester, then add solvent acetic acid 560g, ZnCl
20.2mol, then add isophytol 1.0 molar part (297.0g), feed intake complete, stir, start heating, start reaction under temperature 60 C condition, in 6.0 hours reaction times, reaction completes.
In reaction solution, add 500g normal hexane, stir evenly, leave standstill, point sub-cloud, supernatant liquid is aobvious deeply orange red, and decompression and solvent recovery normal hexane, obtains sample dl-alpha-tocopherol acetic ester 395.0g.
Lower floor's liquid decompression and solvent recovery acetic acid, obtains applying mechanically catalyzer 27.5g, applies mechanically acetic acid 535g; Above-mentioned recovery normal hexane obtains 465g.
Detect dl-alpha-tocopherol acetic ester sample, dl-alpha-tocopherol content 0.12%, dl-alpha-tocopherol acetate content 75.83%, obtaining technological experiment yield is 63.45%.
Solvent acetic acid content 97.6% is applied mechanically in detection, yield 93.2%; Catalyst Z nCl is applied mechanically in detection
2content 94.3%, yield 96%, catalyst recovery effect is better.
Can be obtained by the Comparison of experiment results of above-described embodiment, embodiment 1 adopts in solvent ethyl acetate, Bronsted acid catalyst hydrochloric acid and Lewis acid catalyst AlCl
3co-catalysis Trimethylhydroquinone diethyl ester and isophytol reaction, directly obtain sample dl-alpha-tocopherol acetic ester, experimental result shows that in sample, dl-alpha-tocopherol acetate content is all higher with experiment yield, and solvolysis is simultaneously less, and catalysts and solvents all obtains good recovering effect.
Compare embodiment 2 and adopt solvent acetic acid, ZnCl
2catalyst Trimethylhydroquinone diethyl ester and isophytol reaction, obtain product dl-alpha-tocopherol acetic ester, experimental result shows that in sample, dl-alpha-tocopherol acetate content is lower, and level of response is poor, and experiment yield is also lower.
Embodiment 3
In reaction flask, add 1.0 molar part (236.5g) Trimethylhydroquinone-1-ethyl ester, then add solvent acetic acid methyl esters 500g, Hydrogen bromide 0.05mol, ZnBr
20.5mol, then add phytol 1.0 molar part (297.0g), feed intake complete, stir, start heating, start reaction under temperature 40 DEG C of conditions, in 4.0 hours reaction times, reaction completes.
In reaction solution, add 100ml water, stir evenly, leave standstill, branch vibration layer, repeat 2 times, organic layer shows orange red, reclaim under reduced pressure organic layer solvent, obtains intermediate dl-alpha-tocopherol 423.1g.
Combining water layer, reclaim under reduced pressure moisture content, obtains applying mechanically catalyzer 151.4g; What above-mentioned organic layer recovery obtained is apply mechanically solvent acetic acid methyl esters 495g.
Detect dl-alpha-tocopherol sample, dl-alpha-tocopherol content 96.82%, obtaining technological experiment yield is 95.20%.
Get above-mentioned intermediate dl-alpha-tocopherol (423.5g) and add zinc powder 4.0g, aceticanhydride 165.0g, stir, be heated to 140 DEG C, react 3.0 hours, reaction completes, reclaim under reduced pressure acetic acid, reclaim to finish to cool/cross and filter zinc powder, obtain product dl-alpha-tocopherol acetic ester 461.5g.
Detect dl-alpha-tocopherol acetic ester sample, dl-alpha-tocopherol content 0.05%, dl-alpha-tocopherol acetate content 96.90%, technological experiment yield is 94.60% (total recovery).
Solvent acetic acid methyl ester content 99.2% is applied mechanically in detection, and solvolysis is little, yield 98.4%; Catalyzer Hydrogen bromide 4.7% is applied mechanically in detection, yield 85%, ZnBr
2content 71.0%, yield 96%, catalyst recovery effect is better.
Embodiment 4 ~ 8
Objective for implementation and the correlation parameter of embodiment 4 ~ 8 is listed in table 1.
Table 1
Embodiment 19
In reaction flask, add 1.0 molar part (236.5g) Trimethylhydroquinone-1-ethyl ester, then add in embodiment 1 and apply mechanically solvent ethyl acetate 695g, apply mechanically catalyzer 36.5g (hydrochloric 8%, AlCl
3content 69.5%), then add isophytol 1.0 molar part (297.0g), feed intake complete, stir, start heating, start reaction under temperature 60 C condition, in 5.0 hours reaction times, reaction completes.
In reaction solution, add 100ml water, stir evenly, leave standstill, branch vibration layer, repeat 2 times, organic layer shows orange red, reclaim under reduced pressure organic layer solvent, obtains intermediate dl-alpha-tocopherol 425.4g.
Combining water layer, reclaim under reduced pressure moisture content, obtains applying mechanically catalyzer 34.7g; What above-mentioned organic layer recovery obtained is apply mechanically solvent ethyl acetate 692g.
Detect dl-alpha-tocopherol sample, dl-alpha-tocopherol content 96.91%, obtaining technological experiment yield is 95.72%.
Get above-mentioned intermediate dl-alpha-tocopherol (425.4g) and add zinc powder 4.0g, aceticanhydride 165.0g, stir, be heated to 140 DEG C, react 3.0 hours, reaction completes, reclaim under reduced pressure acetic acid, reclaim to finish to cool/cross and filter zinc powder, obtain product dl-alpha-tocopherol acetic ester 463.6g.
Detect dl-alpha-tocopherol acetic ester sample, dl-alpha-tocopherol content 0.07%, dl-alpha-tocopherol acetate content 96.57%, technological experiment yield is 94.71% (total recovery).
Solvent ethyl acetate content 98.7% is applied mechanically in detection, and solvolysis is little, yield 98.9%; Hydrochloric 7.5% is applied mechanically in detection, yield 89%, AlCl
3content 69.0%, yield 94%, catalyst recovery effect is better.
The present invention is illustrated by embodiment above, but, should be appreciated that the present invention is not limited to particular example as described herein and embodiment.The object comprising these particular example and embodiment is here to help those of skill in the art to put into practice the present invention.Any those of skill in the art are easy to be further improved without departing from the spirit and scope of the present invention and perfect, therefore the present invention is only subject to the content of the claims in the present invention and the restriction of scope, and its intention contains and is allly included in alternatives in the spirit and scope of the invention that limited by appendix claim and equivalent.
Claims (10)
1. the preparation method of a dl-alpha-tocopherol acetic ester, described preparation method with Trimethylhydroquinone diethyl ester (I) or Trimethylhydroquinone-4-ethyl ester (II) for raw material, Bronsted acid and Lewis acid are catalyzer, in esters solvent directly and phytol (III) or isophytol (IV) or phytol derivative (V) carry out condensation reaction and obtain dl-alpha-tocopherol acetic ester or dl-alpha-tocopherol, wherein dl-alpha-tocopherol acetic acid or the further esterification of acetic anhydride obtain dl-alpha-tocopherol acetic ester, wherein:
The structural formula of Trimethylhydroquinone diethyl ester (I) or Trimethylhydroquinone-4-ethyl ester (II) is as follows:
The structural formula of isophytol (III) or phytol (IV) or phytol derivative (V) is as follows:
R in phytol derivative (V) structural formula
1group comprises hydroxyl, halogen, acetoxyl group, benzoyloxy, mesyloxy, ethanesulfonyloxy group, phenylsulfonyloxy or tosyloxy.
2. method as claimed in claim 1, it is characterized in that, described Bronsted acid is selected from least one in hydrochloric acid, Hydrogen bromide, phosphoric acid, sulfuric acid and tosic acid, and described Lewis acid is selected from least one in aluminum chloride, alchlor, aluminium hydroxide, aluminum oxide, iron trichloride, ferric bromide, hydrogenation iron, ferric oxide, zinc chloride, zinc bromide, zinc hydroxide, hydroxy chlorination zinc and hydroxyl zinc bromide.
3. method as claimed in claim 1, it is characterized in that, described esters solvent is low-grade fatty acid ester R
2cOOR
3and/or carbonic ether, wherein, R
2representative has the lower alkyl alkyl of 1 ~ 4 carbon atom, R
3representative has the lower alkyl alkyl of 1 ~ 5 carbon atom.
4. method as claimed in claim 3, is characterized in that, described low-grade fatty acid ester R
2cOOR
3be selected from least one in methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert.-butyl acetate, n-amyl acetate, Isoamyl Acetate FCC, sec-amyl acetate, tert.-amyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl isobutyrate, methyl valerate, Ethylisovalerate and PIVALIC ACID CRUDE (25) ethyl ester; Described carbonic ether is selected from least one in methylcarbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl ester, ethylene carbonate, Texacar PC.
5. method as claimed in claim 1, it is characterized in that, described Bronsted acid is 0.05 ~ 0.5: 1 with the mole ratio of Trimethylhydroquinone diethyl ester or Trimethylhydroquinone-1-ethyl ester, and described Lewis acid is 0.2 ~ 1.0: 1 with the mole ratio of Trimethylhydroquinone diethyl ester or Trimethylhydroquinone-1-ethyl ester.
6. method as claimed in claim 1, it is characterized in that, the weight of described esters solvent is 1.5 ~ 6 times of the weight of Trimethylhydroquinone diethyl ester or Trimethylhydroquinone-1-ethyl ester.
7. method as claimed in claim 1, it is characterized in that, the mole ratio of phytol or isophytol and Trimethylhydroquinone diethyl ester or Trimethylhydroquinone-1-ethyl ester is 0.9 ~ 1.1: 1.
8. method as claimed in claim 1, it is characterized in that, the temperature of condensation reaction is 30 ~ 80 DEG C.
9. method as claimed in claim 1, it is characterized in that, the time of condensation reaction is 2 ~ 8 hours.
10. method as claimed in claim 1, is characterized in that, after completion of the condensation reaction through water extraction and concentrated after, catalyzer and reaction solvent can reclaim and recycle again.
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| 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 |
| CN114940668A (en) * | 2022-03-23 | 2022-08-26 | 万华化学集团股份有限公司 | Preparation of catalyst and application of catalyst in synthesis of vitamin E acetate |
| CN114989125A (en) * | 2022-05-30 | 2022-09-02 | 万华化学(四川)有限公司 | Preparation method of low-color-number vitamin E acetate |
| 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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Cited By (9)
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| 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 |
| CN108203425A (en) * | 2016-12-20 | 2018-06-26 | 浙江医药股份有限公司新昌制药厂 | A kind of preparation method of dl- alpha tocopherols 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 |
| CN109705082B (en) * | 2018-12-19 | 2021-04-20 | 万华化学集团股份有限公司 | Method for preparing vitamin E acetate |
| CN114940668A (en) * | 2022-03-23 | 2022-08-26 | 万华化学集团股份有限公司 | Preparation of catalyst and application of catalyst in synthesis of vitamin E acetate |
| CN114940668B (en) * | 2022-03-23 | 2023-09-19 | 万华化学集团股份有限公司 | Preparation of catalyst and application of catalyst in vitamin E acetate synthesis |
| CN114989125A (en) * | 2022-05-30 | 2022-09-02 | 万华化学(四川)有限公司 | Preparation method of low-color-number vitamin E acetate |
| 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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