CN102336732A - Method for preparing vitamin E ethyl acetate in one kettle way - Google Patents
Method for preparing vitamin E ethyl acetate in one kettle way Download PDFInfo
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- CN102336732A CN102336732A CN201110198791XA CN201110198791A CN102336732A CN 102336732 A CN102336732 A CN 102336732A CN 201110198791X A CN201110198791X A CN 201110198791XA CN 201110198791 A CN201110198791 A CN 201110198791A CN 102336732 A CN102336732 A CN 102336732A
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Abstract
The invention discloses a method for preparing vitamin E ethyl acetate with in a one kettle way. In the method, the vitamin E ethyl acetate is prepared from trimethylhydroquinone diethyl ester serving as a raw material by using trimethylhydroquinone. The method comprises the following steps of: undergoing an ester exchange reaction on trimethylhydroquinone diethyl ester and fatty alcohol under the catalyst action of haloid acid to obtain trimethylhydroquinone; directly condensing and dehydrating the trimethylhydroquinone and heterophytic alcohol without separating or purifying to obtain DL-alpha-tocopheryl; and undergoing an esterification reaction on the DL-alpha-tocopheryl and acetic anhydride to obtain the vitamin E ethyl acetate, wherein a catalyst in the production method can be used mechanically and circularly. The method is easy and convenient to operate, has low production difficulty and low manufacturing cost, and is suitable for large-scale industrial production; and vitamin E ethyl acetate is prepared in an environmentally-friendly way at high yield and high purity.
Description
It is the raw material one kettle way prepares vitamin e acetate through Trimethylhydroquinone working method with the Trimethylhydroquinone diethyl ester that technical field the present invention relates to a kind of.
Background technology vitamin E (Vitamin E) is the general name of different isomerization body in the Viteolin.Occurring in nature exists 4 types Viteolin, promptly α-, β-, γ-, Delta-Tocopherol, usually said vitamin E is meant alpha-tocopherol; Because have three chiral centres, its chemical name is (2R, 4 ' R; 8 ' R)-alpha-tocopherol; Be generally designated as R, R, R-alpha-tocopherol or D-alpha-tocopherol; Mostly industry synthetic vitamin E is the mixture of its 8 kinds of isomer coexistences, therefore is called as all-rac-alpha-tocopherol or DL-alpha-tocopherol.
Vitamin E is as the essential material of a kind of humans and animals, have other material not available, be the necessary biological activity of organism.Discover that the major function of vitamin E has: 1) antioxygenation; 2) improve body's immunological function; 3) antitumous effect; 4) antisterility function; 5) treatment skin disorders; 6) other effects, as promote that tissue respiration, hormone are synthetic, nucleic acid metabolism etc.The power formulations of vitamin e acetate and suitable WHITE CARBON BLACK is as fodder additives, and the market requirement is huge.
Synthesising complex E carries out Friedel-Crafts type condensation ring-closure reaction by Trimethylhydroquinone and different vegetable alcohol and makes in the presence of an acidic catalysts such as zinc chloride; Esterification obtains the vitamin e acetate (US2411969 that uses in stable storing, the commerce then; US3708505, US4239691, US5523420; EP0694541), synthetic route is following:
There is following defective in these methods: the raw material Trimethylhydroquinone has serious human allergy's problem, brings hidden danger to safety in production; The Trimethylhydroquinone poor stability is difficult for storing; When use and a large amount of zinc chloride of extracting and separating, produce great amount of wastewater and be difficult for handling, environmental protection pressure is big.
Also there are bibliographical information different vegetable alcohol and Trimethylhydroquinone diethyl ester directly to carry out condensation reaction; Trimethylhydroquinone diethyl ester (TMHQ-DA) as the major advantage of the synthetic Equivalent of TMHQ is: the ethanoyl that in the vitamin e acetate finished product, exists is Already in the TMHQ-DA molecule; And can be through ingenious control reaction; TMHQ-DA and different vegetable alcohol condensation are directly obtained vitamin e acetate; And needn't independently carry out esterification subsequently in the reactions step with acetic anhydride stoichiometric quantity or that surpass stoichiometric quantity; But up to the present, do not find that also economic method can be carried out Trimethylhydroquinone diethyl ester (TMHQ-DA) and the direct condensation of different vegetable alcohol with sufficiently high yield, and directly obtain vitamin e acetate.Have among the FR-A2259822 (DE-OS 2404621) to relate to this type of reaction, but describe in the document under solid acid and the yield of the condensation reaction synthesising complex E of different vegetable alcohol also only have an appointment 41%, and do not generate corresponding acetic ester.
Consider from the yield aspect; With Trimethylhydroquinone diethyl ester reaction more successful JP-OS 51-8-859 arranged, its utilize Trimethylhydroquinone or its ester under zinc chloride and different vegetable alcohol react, this is reflected under the temperature more than 100 ℃ and generates alpha-tocopherol; This method considers it is economical from the yield of gained; But its shortcoming is a wastewater problem, and this problem is owing to a large amount of zinc chloride of use causes, the simple recycle of these solder(ing)acids of extraction back gained is impossible; And the water that produces in the reaction process can make catalyst deactivation, causes once more the reduction of reaction yield and the decline of quality product.
The effective means of Trimethylhydroquinone diethyl ester reaction is in the news in DE-OS 19757124.7, and this method is the binary catalyst system that comprises zinc chloride and haloid acid of in various inert aprotic solvents, using.The aftertreatment here is that water is carried whole catalyzer and carried out mutually after the condensation, and the processing behind the acetylization reaction subsequently need be carried through water equally and extract catalyzer once more.When use contains ester solvent; The existence of water causes other problem in the reaction, promptly except the saponification that TMHQ-DA takes place in position, the partly-hydrolysed result of solvent is arranged also; Like this; Produce corresponding organic acid and alcohol as the ester of solvent, they must remove from product or gather returning in the circulation means of solvent through the separation method of costliness, so not only can cause the decline of quality product but also cause the increase of production cost.
Chinese patent CN01104390 " method for preparing alpha-tocopherol acetate " discloses a kind of method that in circulation method, prepares alpha-tocopherol acetate; It discloses the preparation method: the alpha-tocopherol that I) obtains at first and the mixture of alpha-tocopherol acetate are used the acetic anhydride esterification, form acetic acid; II) be reproduced through the catalyst acetic acid solution that obtains after the extraction; The regeneration soln that contains acetic acid is returned in the reaction; And III) merge at I) and II) in the catalyst acetic acid solution that contains active catalyst component zinc halide and haloid acid that obtains concentrated, and be returned with liquid form and react.Method catalyzer is capable of circulation applies mechanically for this, has alleviated the pressure of environmental protection.But there is the problem that separation efficiency is low, energy consumption is high in acetic acid and the water sepn process; It is high to concentrate the catalyst acetic acid solution energy consumption that contains active catalyst component zinc halide and haloid acid; The bad control of catalyst system moisture of circulation usefulness causes catalyzer five-ring isomer of alpha-tocopherol in recycled subsequently to raise gradually; Even unqualified, in fact and be not suitable for suitability for industrialized production so this method.
Summary of the invention is for overcoming above defective; The present invention provides a kind of one kettle way to prepare the working method of vitamin e acetate; It gets Trimethylhydroquinone with fatty alcohol generation transesterification reaction with the Trimethylhydroquinone diethyl ester under the haloid acid katalysis; Trimethylhydroquinone without separation and purification directly and the different vegetable alcohol condensation dewater the DL-alpha-tocopherol, DL-alpha-tocopherol and aceticanhydride generation esterification get vitamin e acetate then.
Technical scheme of the present invention is: one kettle way prepares the working method of vitamin e acetate, and said working method may further comprise the steps:
1) preparation of Trimethylhydroquinone: the Trimethylhydroquinone diethyl ester of getting 1.0 molar part; The fatty alcohol of adding 2-10 molar part, the haloid acid of 0.2-0.8 molar part feed nitrogen protection in reaction flask, be warming up to 60 ± 5 ℃; Insulation reaction 1.5-2h; Reaction finishes, decompression and solvent recovery, and residue is Trimethylhydroquinone;
2) preparation of DL-alpha-tocopherol: in above-mentioned gained residue, add zinc halide, Glacial acetic acid min. 99.5, haloid acid, zinc powder, be warming up to 60 ± 5 ℃, drip different vegetable alcohol; Drip and finish, continue at 60 ± 5 ℃ and stir 3-5h, standing demix; The acetate layer that lower floor contains catalyzer and unreacting material after dewatering by recycled again to next batch; Upper strata Viteolin layer directly is used for next step esterification, and wherein, the mol ratio of zinc halide and Trimethylhydroquinone diethyl ester is 0.3-0.5: 1; The weight ratio of Glacial acetic acid min. 99.5 and Trimethylhydroquinone diethyl ester is 2-4: 1; The mol ratio of haloid acid and Trimethylhydroquinone diethyl ester is 0.2-0.8: 1, and the weight ratio of zinc powder and Trimethylhydroquinone diethyl ester is 0.005-0.015: 1, the mol ratio of different vegetable alcohol and Trimethylhydroquinone diethyl ester is 0.95-1.15: 1;
3) preparation of vitamin e acetate: in above-mentioned gained Viteolin layer, add zinc powder, acetic anhydride, be warming up to 120-130 ℃, reaction 2.5-3h, reaction finishes; Acetic acid and acetic anhydride are reclaimed in rectification under vacuum, in residue, add sherwood oil then, and water stirs 15-30min; Standing demix, water layer merge organic layer, the water washed twice with Petroleum ether extraction twice; 50-60 ℃ of concentrating under reduced pressure reclaims sherwood oil, concentrates and finishes, and gets vitamin e acetate; Wherein, the weight ratio of zinc powder and Trimethylhydroquinone diethyl ester is 0.005-0.015: 1, and the weight ratio of acetic anhydride and Trimethylhydroquinone diethyl ester is 0.5-1: 1.
Described fatty alcohol is selected a kind of in ethanol, n-propyl alcohol, Virahol, propyl carbinol, the isopropylcarbinol for use.
Described haloid acid is hydrochloric acid or Hydrogen bromide.
Said zinc halide is zinc chloride or zinc bromide.
Acetate layer in the said step 2 recycled after dewatering adds fresh zinc powder and the haloid acid compensate for catalyst concentration of original vol 20-50% more than 2 times at every turn during recycled; Need not add zinc halide just can use.
The dehydration operation of acetate layer is in the said step 2: in acetate layer, add the acetic anhydride that reclaims in the said step 3, regulate moisture≤1.5% in the acetate layer.
Described Trimethylhydroquinone second diester makes by the disclosed preparation method of patent of invention ZL99100672.0 " preparation method of Trimethylhydroquinone second diester and Trimethylhydroquinone ".
Synthetic route of the present invention is following:
The invention has the beneficial effects as follows:
1) adopts aforesaid method; The present invention only need use a spot of haloid acid, with fatty alcohol the Trimethylhydroquinone diethyl ester is carried out transesterify and prepares Trimethylhydroquinone, and this preparation method need not use a large amount of acid; Therefore can not produce a large amount of waste water, pollution on the environment is little;
2) with fatty alcohol Trimethylhydroquinone second diester is carried out transesterify and prepare Trimethylhydroquinone, used fatty alcohol equal solvent can be used through the simple distillation recovery set;
3) Trimethylhydroquinone second diester raw material preparation and highly stable easily, normal temperature store down and get final product, and also having avoided direct employing Trimethylhydroquinone is human allergy's problem that raw material brought;
4) adopt the Trimethylhydroquinone diethyl ester to carry out condensation reaction than directly adopting Trimethylhydroquinone diethyl ester and different vegetable alcohol to carry out the condensation reaction better effects if through Trimethylhydroquinone and different vegetable alcohol; Solved and used the Trimethylhydroquinone diethyl ester to cause the low problem of finished product vitamin e acetate content as raw material, the vitamin e acetate that obtains not only satisfied the specification of quality of doing 93%Ve oil and feed Ve powder but also satisfied and done the oily specification of quality of 98%Ve elaboration;
5) the solvent Glacial acetic acid min. 99.5 selected for use of step of condensation can make reaction take place with good yield, and the reaction times is short, is applicable to suitability for industrialized production;
6) utilize the immiscible characteristic of Glacial acetic acid min. 99.5 and Viteolin; And unreacted raw material and catalyzer are at the Glacial acetic acid min. 99.5 layer; Make the condensation reaction aftertreatment become very simple, the acetate layer that contains catalyzer and unreacting material after simple dehydration quilt again recycled to next batch.
Therefore, the present invention is easy and simple to handle, and the production difficulty is little, and low cost of manufacture with high yield of very simple and environment amenable mode and high purity ground preparation vitamin e acetate, is fit to large-scale industrial production.
The working method that embodiment one kettle way according to the invention prepares vitamin e acetate may further comprise the steps:
1) preparation of Trimethylhydroquinone: the Trimethylhydroquinone diethyl ester of getting 1.0 molar part; The fatty alcohol of adding 2-10 molar part, the haloid acid of 0.2-0.8 molar part feed nitrogen protection in reaction flask, be warming up to 60 ± 5 ℃; Insulation reaction 1.5-2h; Reaction finishes, decompression and solvent recovery, and residue is Trimethylhydroquinone;
2) preparation of DL-alpha-tocopherol: in above-mentioned gained residue, add zinc halide, Glacial acetic acid min. 99.5, haloid acid, zinc powder, be warming up to 60 ± 5 ℃, drip different vegetable alcohol; Drip and finish, continue at 60 ± 5 ℃ and stir 3-5h, standing demix; The acetate layer that lower floor contains catalyzer and unreacting material after dewatering by recycled again to next batch; Upper strata Viteolin layer directly is used for next step esterification, and wherein, the mol ratio of zinc halide and Trimethylhydroquinone diethyl ester is 0.3-0.5: 1; The weight ratio of Glacial acetic acid min. 99.5 and Trimethylhydroquinone diethyl ester is 2-4: 1; The mol ratio of haloid acid and Trimethylhydroquinone diethyl ester is 0.2-0.8: 1, and the weight ratio of zinc powder and Trimethylhydroquinone diethyl ester is 0.005-0.015: 1, the mol ratio of different vegetable alcohol and Trimethylhydroquinone diethyl ester is 0.95-1.15: 1;
3) preparation of vitamin e acetate: in above-mentioned gained Viteolin layer, add zinc powder, acetic anhydride, be warming up to 120-130 ℃, reaction 2.5-3h, reaction finishes; Acetic acid and acetic anhydride are reclaimed in rectification under vacuum, in residue, add sherwood oil then, and water stirs 15-30min; Standing demix, water layer merge organic layer, the water washed twice with Petroleum ether extraction twice; 50-60 ℃ of concentrating under reduced pressure reclaims sherwood oil, concentrates and finishes, and gets vitamin e acetate; Wherein, the weight ratio of zinc powder and Trimethylhydroquinone diethyl ester is 0.005-0.015: 1, and the weight ratio of acetic anhydride and Trimethylhydroquinone diethyl ester is 0.5-1: 1.
Described fatty alcohol is selected a kind of in ethanol, n-propyl alcohol, Virahol, propyl carbinol, the isopropylcarbinol for use.
Described haloid acid is hydrochloric acid or Hydrogen bromide.
Said zinc halide is zinc chloride or zinc bromide.
Acetate layer in the said step 2 recycled after dewatering adds fresh zinc powder and the haloid acid compensate for catalyst concentration of original vol 20-50% more than 2 times at every turn during recycled; Need not add zinc halide just can use.
The dehydration operation of acetate layer is in the said step 2: in acetate layer, add the acetic anhydride that reclaims in the said step 3, regulate moisture≤1.5% in the acetate layer.
The present invention does further to set forth through following examples:
Embodiment 1
In reaction flask, add Trimethylhydroquinone second diester 100g, absolute ethyl alcohol 49.4mL, concentrated hydrochloric acid 8.6g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims ethanol, and recovery finishes, and in residue, adds zinc chloride 17.3g, Glacial acetic acid min. 99.5 200g, concentrated hydrochloric acid 8.6g, zinc powder 0.5g, is warming up to 55 ℃, drips different vegetable alcohol 119.2g; Drip and finish, continue at 55 ℃ and stir 3h, standing demix adds zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 15min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 220g.
Embodiment 2
In reaction flask, add Trimethylhydroquinone second diester 100g, absolute ethyl alcohol 247mL, concentrated hydrochloric acid 34.4g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims ethanol, and recovery finishes, and in residue, adds zinc chloride 28.8g, Glacial acetic acid min. 99.5 400g, concentrated hydrochloric acid 34.4g, zinc powder 1.5g, is warming up to 65 ℃; Drip different vegetable alcohol 144.3g, drip and finish, continue at 65 ℃ and stir 5h, standing demix; Add zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃, reaction 3h, reaction finishes; Acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL, water 150mL; Stir 30min, standing demix, water layer extracts for 80mL/ time with sherwood oil, extracts 2 times.Merge organic layer, 100mL/ washing of water washed 2 times, and 60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 219.5g.
Embodiment 3
In reaction flask, add Trimethylhydroquinone second diester 100g, absolute ethyl alcohol 148.2mL, concentrated hydrochloric acid 21.5g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims ethanol, and recovery finishes, and in residue, adds zinc chloride 23g, Glacial acetic acid min. 99.5 300g, concentrated hydrochloric acid 21.5g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 222g.
Embodiment 4
In reaction flask, add Trimethylhydroquinone second diester 100g, absolute ethyl alcohol 49.4mL, Hydrogen bromide 14.2g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims ethanol, and recovery finishes, and in residue, adds zinc bromide 28.6g, Glacial acetic acid min. 99.5 200g, Hydrogen bromide 14.2g, zinc powder 0.5g, is warming up to 55 ℃; Drip different vegetable alcohol 119.2g, drip and finish, continue at 55 ℃ and stir 3h, standing demix; Add zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃, reaction 2.5h, reaction finishes; Acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL, water 150mL; Stir 15min, standing demix, water layer extracts for 80mL/ time with sherwood oil, extracts 2 times.Merge organic layer, 100mL/ washing of water washed 2 times, and 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 221g.
Embodiment 5
In reaction flask, add Trimethylhydroquinone second diester 100g, absolute ethyl alcohol 247mL, Hydrogen bromide 57g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims ethanol, and recovery finishes, and in residue, adds zinc bromide 47.6g, Glacial acetic acid min. 99.5 400g, Hydrogen bromide 57g, zinc powder 1.5g, is warming up to 65 ℃, drips different vegetable alcohol 144.3g; Drip and finish, continue at 65 ℃ and stir 5h, standing demix adds zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 223g.
Embodiment 6
In reaction flask, add Trimethylhydroquinone second diester 100g, absolute ethyl alcohol 148.2mL, Hydrogen bromide 35.6g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims ethanol, and recovery finishes, and in residue, adds zinc bromide 38.1g, Glacial acetic acid min. 99.5 300g, Hydrogen bromide 35.6g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 219.6g.
Embodiment 7
In reaction flask, add Trimethylhydroquinone second diester 100g, absolute ethyl alcohol 160mL, Hydrogen bromide 39g, finish, feed nitrogen protection, heat up 60 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims ethanol, adds Glacial acetic acid min. 99.5 layer, Hydrogen bromide 7.8g, zinc powder 0.2g after the above-mentioned dehydration then, is warming up to 60 ℃, drips different vegetable alcohol 125.5g, drips and finishes; Continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, add sherwood oil 200mL; Water 150mL stirs 20min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times.50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate and finish, heavy 227g.
Add the aceticanhydride 15g that reclaims in the present embodiment in the Glacial acetic acid min. 99.5 layer in embodiment 6, normal temperature stirs 30min down, and moisture 1.0% is surveyed in sampling.
Condensation step need not be added zinc bromide; Only need add the fresh zinc powder and the Hydrogen bromide of original vol 20%; React in a manner described more afterwards, in this way, acetic acid does not carry out intermediate purification only need pass through simple dehydration to moisture≤1.5%; As solvent 9 times, the total recovery of all above-mentioned 10 secondary responses is 95% (calculating based on used Trimethylhydroquinone diethyl ester) with acetic acid.
Embodiment 8
In reaction flask, add Trimethylhydroquinone second diester 100g, n-propyl alcohol 63.6mL, concentrated hydrochloric acid 8.6g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims n-propyl alcohol, and recovery finishes, and in residue, adds zinc chloride 17.3g, Glacial acetic acid min. 99.5 200g, concentrated hydrochloric acid 8.6g, zinc powder 0.5g, is warming up to 55 ℃, drips different vegetable alcohol 119.2g; Drip and finish, continue at 55 ℃ and stir 3h, standing demix adds zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 15min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 221g.
Embodiment 9
In reaction flask, add Trimethylhydroquinone second diester 100g, n-propyl alcohol 318mL, concentrated hydrochloric acid 34.4g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims n-propyl alcohol, and recovery finishes, and in residue, adds zinc chloride 28.8g, Glacial acetic acid min. 99.5 400g, concentrated hydrochloric acid 34.4g, zinc powder 1.5g, is warming up to 65 ℃, drips different vegetable alcohol 144.3g; Drip and finish, continue at 65 ℃ and stir 5h, standing demix adds zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times.60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 230g.
Embodiment 10
In reaction flask, add Trimethylhydroquinone second diester 100g, n-propyl alcohol 190.9mL, concentrated hydrochloric acid 21.5g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims n-propyl alcohol, and recovery finishes, and in residue, adds zinc chloride 23g, Glacial acetic acid min. 99.5 300g, concentrated hydrochloric acid 21.5g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times.55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 225g.
Embodiment 11
In reaction flask, add Trimethylhydroquinone second diester 100g, n-propyl alcohol 63.6mL, Hydrogen bromide 14.2g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims n-propyl alcohol, and recovery finishes, and in residue, adds zinc bromide 28.6g, Glacial acetic acid min. 99.5 200g, Hydrogen bromide 14.2g, zinc powder 0.5g, is warming up to 55 ℃, drips different vegetable alcohol 119.2g; Drip and finish, continue at 55 ℃ and stir 3h, standing demix adds zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 15min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 219.8g.
Embodiment 12
In reaction flask, add Trimethylhydroquinone second diester 100g, n-propyl alcohol 318mL, Hydrogen bromide 57g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims n-propyl alcohol, and recovery finishes, and in residue, adds zinc bromide 47.6g, Glacial acetic acid min. 99.5 400g, Hydrogen bromide 57g, zinc powder 1.5g, is warming up to 65 ℃, drips different vegetable alcohol 144.3g; Drip and finish, continue at 65 ℃ and stir 5h, standing demix adds zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 224.9g.
Embodiment 13
In reaction flask, add Trimethylhydroquinone second diester 100g, n-propyl alcohol 190.9mL, Hydrogen bromide 35.6g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims n-propyl alcohol, and recovery finishes, and in residue, adds zinc bromide 38.1g, Glacial acetic acid min. 99.5 300g, Hydrogen bromide 35.6g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times.55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 223.6g.
Embodiment 14
In reaction flask, add Trimethylhydroquinone second diester 100g, Virahol 64.8mL, concentrated hydrochloric acid 8.6g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims Virahol, and recovery finishes, and in residue, adds zinc chloride 17.3g, Glacial acetic acid min. 99.5 200g, concentrated hydrochloric acid 8.6g, zinc powder 0.5g, is warming up to 55 ℃, drips different vegetable alcohol 119.2g; Drip and finish, continue at 55 ℃ and stir 3h, standing demix adds zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 15min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 222g.
Embodiment 15
In reaction flask, add Trimethylhydroquinone second diester 100g, Virahol 324mL, concentrated hydrochloric acid 34.4g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims Virahol, and recovery finishes, and in residue, adds zinc chloride 28.8g, Glacial acetic acid min. 99.5 400g, concentrated hydrochloric acid 34.4g, zinc powder 1.5g, is warming up to 65 ℃, drips different vegetable alcohol 144.3g; Drip and finish, continue at 65 ℃ and stir 5h, standing demix adds zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 222.7g.
Embodiment 16
In reaction flask, add Trimethylhydroquinone second diester 100g, Virahol 194.4mL, concentrated hydrochloric acid 21.5g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims Virahol, and recovery finishes, and in residue, adds zinc chloride 23g, Glacial acetic acid min. 99.5 300g, concentrated hydrochloric acid 21.5g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 220.6g.
Embodiment 17
In reaction flask, add Trimethylhydroquinone second diester 100g, Virahol 64.8mL, Hydrogen bromide 14.2g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims Virahol, and recovery finishes, and in residue, adds zinc bromide 28.6g, Glacial acetic acid min. 99.5 200g, Hydrogen bromide 14.2g, zinc powder 0.5g, is warming up to 55 ℃, drips different vegetable alcohol 119.2g; Drip and finish, continue at 55 ℃ and stir 3h, standing demix adds zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 15min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 221.9g.
Embodiment 18
In reaction flask, add Trimethylhydroquinone second diester 100g, Virahol 324mL, Hydrogen bromide 57g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims Virahol, and recovery finishes, and in residue, adds zinc bromide 47.6g, Glacial acetic acid min. 99.5 400g, Hydrogen bromide 57g, zinc powder 1.5g, is warming up to 65 ℃, drips different vegetable alcohol 144.3g; Drip and finish, continue at 65 ℃ and stir 5h, standing demix adds zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 220.2g.
Embodiment 19
In reaction flask, add Trimethylhydroquinone second diester 100g, Virahol 194.4mL, Hydrogen bromide 35.6g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims Virahol, and recovery finishes, and in residue, adds zinc bromide 38.1g, Glacial acetic acid min. 99.5 300g, Hydrogen bromide 35.6g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 221.8g.
Embodiment 20
In reaction flask, add Trimethylhydroquinone second diester 100g, propyl carbinol 77.4mL, concentrated hydrochloric acid 8.6g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims propyl carbinol, and recovery finishes, and in residue, adds zinc chloride 17.3g, Glacial acetic acid min. 99.5 200g, concentrated hydrochloric acid 8.6g, zinc powder 0.5g, is warming up to 55 ℃, drips different vegetable alcohol 119.2g; Drip and finish, continue at 55 ℃ and stir 3h, standing demix adds zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 15min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 224.0g.
Embodiment 21
In reaction flask, add Trimethylhydroquinone second diester 100g, propyl carbinol 387mL, concentrated hydrochloric acid 34.4g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims propyl carbinol, and recovery finishes, and in residue, adds zinc chloride 28.8g, Glacial acetic acid min. 99.5 400g, concentrated hydrochloric acid 34.4g, zinc powder 1.5g, is warming up to 65 ℃, drips different vegetable alcohol 144.3g; Drip and finish, continue at 65 ℃ and stir 5h, standing demix adds zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 223.2g.
Embodiment 22
In reaction flask, add Trimethylhydroquinone second diester 100g, propyl carbinol 232.2mL, concentrated hydrochloric acid 21.5g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims propyl carbinol, and recovery finishes, and in residue, adds zinc chloride 23g, Glacial acetic acid min. 99.5 300g, concentrated hydrochloric acid 21.5g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 221.9g.
Embodiment 23
In reaction flask, add Trimethylhydroquinone second diester 100g, propyl carbinol 77.4mL, Hydrogen bromide 14.2g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims propyl carbinol, and recovery finishes, and in residue, adds zinc bromide 28.6g, Glacial acetic acid min. 99.5 200g, Hydrogen bromide 14.2g, zinc powder 0.5g, is warming up to 55 ℃, drips different vegetable alcohol 119.2g; Drip and finish, continue at 55 ℃ and stir 3h, standing demix adds zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 15min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 220.3g.
Embodiment 24
In reaction flask, add Trimethylhydroquinone second diester 100g, propyl carbinol 387mL, Hydrogen bromide 57g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims propyl carbinol, and recovery finishes, and in residue, adds zinc bromide 47.6g, Glacial acetic acid min. 99.5 400g, Hydrogen bromide 57g, zinc powder 1.5g, is warming up to 65 ℃, drips different vegetable alcohol 144.3g; Drip and finish, continue at 65 ℃ and stir 5h, standing demix adds zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 220.9g.
Embodiment 25
In reaction flask, add Trimethylhydroquinone second diester 100g, propyl carbinol 232.2mL, Hydrogen bromide 35.6g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims propyl carbinol, and recovery finishes, and in residue, adds zinc bromide 38.1g, Glacial acetic acid min. 99.5 300g, Hydrogen bromide 35.6g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 221.5g.
Embodiment 26
In reaction flask, add Trimethylhydroquinone second diester 100g, isopropylcarbinol 78.4mL, concentrated hydrochloric acid 8.6g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims isopropylcarbinol, and recovery finishes, and in residue, adds zinc chloride 17.3g, Glacial acetic acid min. 99.5 200g, concentrated hydrochloric acid 8.6g, zinc powder 0.5g, is warming up to 55 ℃, drips different vegetable alcohol 119.2g; Drip and finish, continue at 55 ℃ and stir 3h, standing demix adds zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 15min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 223.0g.
Embodiment 27
In reaction flask, add Trimethylhydroquinone second diester 100g, isopropylcarbinol 392mL, concentrated hydrochloric acid 34.4g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims isopropylcarbinol, and recovery finishes, and in residue, adds zinc chloride 28.8g, Glacial acetic acid min. 99.5 400g, concentrated hydrochloric acid 34.4g, zinc powder 1.5g, is warming up to 65 ℃, drips different vegetable alcohol 144.3g; Drip and finish, continue at 65 ℃ and stir 5h, standing demix adds zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 220.4g.
Embodiment 28
In reaction flask, add Trimethylhydroquinone second diester 100g, isopropylcarbinol 235.2mL, concentrated hydrochloric acid 21.5g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims isopropylcarbinol, and recovery finishes, and in residue, adds zinc chloride 23g, Glacial acetic acid min. 99.5 300g, concentrated hydrochloric acid 21.5g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 220.7g.
Embodiment 29
In reaction flask, add Trimethylhydroquinone second diester 100g, isopropylcarbinol 78.4mL, Hydrogen bromide 14.2g, finish, feed nitrogen protection, heat up 55 ℃, reaction 1.5h; Concentrating under reduced pressure reclaims isopropylcarbinol, and recovery finishes, and in residue, adds zinc bromide 28.6g, Glacial acetic acid min. 99.5 200g, Hydrogen bromide 14.2g, zinc powder 0.5g, is warming up to 55 ℃, drips different vegetable alcohol 119.2g; Drip and finish, continue at 55 ℃ and stir 3h, standing demix adds zinc powder 0.5g, aceticanhydride 50g in the Viteolin layer of upper strata, be warming up to 120 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 15min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 50 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 221.6g.
Embodiment 30
In reaction flask, add Trimethylhydroquinone second diester 100g, isopropylcarbinol 392mL, Hydrogen bromide 57g, finish, feed nitrogen protection, heat up 65 ℃, reaction 2h; Concentrating under reduced pressure reclaims isopropylcarbinol, and recovery finishes, and in residue, adds zinc bromide 47.6g, Glacial acetic acid min. 99.5 400g, Hydrogen bromide 57g, zinc powder 1.5g, is warming up to 65 ℃, drips different vegetable alcohol 144.3g; Drip and finish, continue at 65 ℃ and stir 5h, standing demix adds zinc powder 1.5g, aceticanhydride 100g in the Viteolin layer of upper strata, be warming up to 130 ℃; Reaction 3h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 60 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 222.4g.
Embodiment 31
In reaction flask, add Trimethylhydroquinone second diester 100g, isopropylcarbinol 235.2mL, Hydrogen bromide 35.6g, finish, feed nitrogen protection, heat up 60 ℃, reaction 2h; Concentrating under reduced pressure reclaims isopropylcarbinol, and recovery finishes, and in residue, adds zinc bromide 38.1g, Glacial acetic acid min. 99.5 300g, Hydrogen bromide 35.6g, zinc powder 1.0g, is warming up to 60 ℃, drips different vegetable alcohol 131.8g; Drip and finish, continue at 60 ℃ and stir 4h, standing demix adds zinc powder 1.0g, aceticanhydride 75g in the Viteolin layer of upper strata, be warming up to 125 ℃; Reaction 2.5h, reaction finishes, and acetic acid and aceticanhydride are reclaimed in rectification under vacuum, and recovery finishes, and in residue, adds sherwood oil 200mL; Water 150mL stirs 30min, standing demix, and water layer extracts for 80mL/ time with sherwood oil; Extract 2 times, merge organic layer, 100mL/ washing of water washed 2 times; 55 ℃ of concentrating under reduced pressure reclaim sherwood oil, concentrate to finish, and get vitamin e acetate 222.7g.
Claims (6)
1. one kettle way prepares the working method of vitamin e acetate, it is characterized in that: said working method may further comprise the steps:
1), the preparation of Trimethylhydroquinone: the Trimethylhydroquinone diethyl ester of getting 1.0 molar part; The fatty alcohol of adding 2-10 molar part, the haloid acid of 0.2-0.8 molar part feed nitrogen protection in reaction flask, be warming up to 60 ± 5 ℃; Insulation reaction 1.5-2h; Reaction finishes, decompression and solvent recovery, and residue is Trimethylhydroquinone;
2), the preparation of DL-alpha-tocopherol: in above-mentioned gained residue, add zinc halide, Glacial acetic acid min. 99.5, haloid acid, zinc powder, be warming up to 60 ± 5 ℃, drip different vegetable alcohol; Drip and finish, continue at 60 ± 5 ℃ and stir 3-5h, standing demix; The acetate layer that lower floor contains catalyzer and unreacting material after dewatering by recycled again to next batch; Upper strata Viteolin layer directly is used for next step esterification, and wherein, the mol ratio of zinc halide and Trimethylhydroquinone diethyl ester is 0.3-0.5: 1; The weight ratio of Glacial acetic acid min. 99.5 and Trimethylhydroquinone diethyl ester is 2-4: 1; The mol ratio of haloid acid and Trimethylhydroquinone diethyl ester is 0.2-0.8: 1, and the weight ratio of zinc powder and Trimethylhydroquinone diethyl ester is 0.005-0.015: 1, the mol ratio of different vegetable alcohol and Trimethylhydroquinone diethyl ester is 0.95-1.15: 1;
3), the preparation of vitamin e acetate: in above-mentioned gained Viteolin layer, add zinc powder, acetic anhydride, be warming up to 120-130 ℃, react 2.5-3h, reaction finishes; Acetic acid and acetic anhydride are reclaimed in rectification under vacuum, in residue, add sherwood oil then, and water stirs 15-30min; Standing demix, water layer merge organic layer, the water washed twice with Petroleum ether extraction twice; 50-60 ℃ of concentrating under reduced pressure reclaims sherwood oil, concentrates and finishes, and gets vitamin e acetate; Wherein, the weight ratio of zinc powder and Trimethylhydroquinone diethyl ester is 0.005-0.015: 1, and the weight ratio of acetic anhydride and Trimethylhydroquinone diethyl ester is 0.5-1: 1.
2. one kettle way according to claim 1 prepares the working method of vitamin e acetate, it is characterized in that: said fatty alcohol is a kind of in ethanol, n-propyl alcohol, Virahol, propyl carbinol, the isopropylcarbinol.
3. one kettle way according to claim 1 prepares the working method of vitamin e acetate, it is characterized in that: said haloid acid is hydrochloric acid or Hydrogen bromide.
4. one kettle way according to claim 1 prepares the working method of vitamin e acetate, it is characterized in that: said zinc halide is zinc chloride or zinc bromide.
5. one kettle way according to claim 1 prepares the working method of vitamin e acetate; It is characterized in that: the recycled after dewatering of the acetate layer in the said step 2 adds fresh zinc powder and the haloid acid compensate for catalyst concentration of original vol 20-50% more than 2 times at every turn during recycled.
6. one kettle way according to claim 1 prepares the working method of vitamin e acetate; It is characterized in that: the dehydration operation of acetate layer is in the said step 2: in acetate layer, add the acetic anhydride that reclaims in the said step 3, regulate moisture≤1.5% in the acetate layer.
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| CN106478581A (en) * | 2016-08-30 | 2017-03-08 | 芜湖华海生物工程有限公司 | A kind of preparation method of Vitwas E |
| 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 |
| CN108409704A (en) * | 2018-01-24 | 2018-08-17 | 上海优合生物科技有限公司 | A kind of preparation method of high-purity tocopherol succinate salt |
| 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 |
| 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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| CN108409704A (en) * | 2018-01-24 | 2018-08-17 | 上海优合生物科技有限公司 | A kind of preparation method of high-purity tocopherol succinate salt |
| 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 |
| 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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