CN105367534B - A method of preparing dl- alpha tocopherol acetate - Google Patents
A method of preparing dl- alpha tocopherol acetate Download PDFInfo
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- CN105367534B CN105367534B CN201410427232.5A CN201410427232A CN105367534B CN 105367534 B CN105367534 B CN 105367534B CN 201410427232 A CN201410427232 A CN 201410427232A CN 105367534 B CN105367534 B CN 105367534B
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- alpha tocopherol
- acetic acid
- aceticanhydride
- tocopherol acetate
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Abstract
The present invention relates to a kind of methods for preparing dl- alpha tocopherol acetate; this method is using the mixture of dl- alpha tocopherol or dl- alpha tocopherol and dl- alpha tocopherol acetate as raw material; use nitrogen-containing basic substance for catalyst; the mixture of acetic acid or aceticanhydride or acetic acid and aceticanhydride is acylating agent, and esterification obtains dl- alpha tocopherol acetate product.Preparation method of the invention shows simply on the whole, and operability is good, and yield is higher, and product quality is preferable, and above there is very little risk in environment and safety.
Description
Technical field
The present invention relates to a kind of preparation method of dl- alpha tocopherol acetate, specifically include raw with dl- alpha tocopherol or dl- α
Educating phenol and dl- alpha tocopherol acetic acid ester admixture is raw material, under nitrogen-containing basic catalyst action, with acetic acid or aceticanhydride or acetic acid
Esterification is carried out with the mixture or acetic acid of aceticanhydride and the mixture of aceticanhydride, obtains dl- alpha tocopherol acetate product.
Technical background
Vitamin E mainly has the function of anti-oxidant, anti-aging, raising immunity, antisterility etc., is mainly used for clinic in early days
On treatment that is infertile and promoting reproduction, now then more for beautifying and anti-aging, free radical resisting oxidation, protect it is red thin
Born of the same parents, protection T lymphocyte improve blood circulation, inhibit platelet aggregation, treatment menopausal syndrome and treatment burn frostbite
Deng actual product is then mainly used in drug, food, cosmetics and feed addictive.
Vitamin E mainly includes natural VE (including d- alpha tocopherol and d- alpha tocopherol acetate etc.) and synthesis dimension
Raw element E (including dl- alpha tocopherol and dl- alpha tocopherol acetate etc.), wherein natural VE mostlys come from mentioning for vegetable oil
It takes, due to being limited by raw material sources, the yield and application range of natural VE are not very big, and main synthesis dimension is given birth to
Plain E is of wide application substantially from the synthesis technology of chemical industry, and yield and demand are all very big.
Dl- alpha tocopherol and dl- alpha tocopherol acetate are the main application forms of synthesising complex E, wherein dl- alpha tocopherol
Due to easy to oxidize not easy to maintain, so being transformed into dl- alpha tocopherol acetate form all generally to be used widely.
Under normal circumstances, dl- alpha tocopherol is transformed into the process of dl- alpha tocopherol acetate, mainly dl- alpha tocopherol with
The esterification that the mixture of acetic acid or aceticanhydride or acetic acid and aceticanhydride carries out, wherein aceticanhydride reactivity is preferable, but higher cost,
Acetic acid reaction activity is poor, but also esterification can be promoted preferably to carry out under certain catalyst action, and cost is relatively low.
The catalyst of esterification generally comprises as sour (strong acid or weak acid), alkali (highly basic or weak base) and non-catalytic reaction
Etc., wherein strong acid and highly basic are not suitable for the reaction of dl- α catalysis tocopherol, because dl- alpha tocopherol is easily oxidized etc. and to destroy,
Lead to color burn, under strong acid or basic conditions, dl- alpha tocopherol or dl- alpha tocopherol acetate etc. are destroyed substantially, finally
Obtained product colour is orange red to black, poor quality, to be unable to get utilization；Weak acid is catalyzed such dl- alpha tocopherol
Esterification catalytic activity is poor, and the extent of reaction is smaller, and yield is lower, and obtained product quality is also poor.
The esterification technique of present dl- alpha tocopherol acetate is generally used the non-catalytic reaction under zinc powder protective effect,
Middle zinc powder primarily serves protection dl- alpha tocopherol or the not oxidized destruction of dl- alpha tocopherol acetate, the esterification reaction temperature of technique
It is higher, commonly reach 130~140 DEG C, acylating agent is aceticanhydride, and the inventory of aceticanhydride is larger, and with this condition acetic acid be difficult with
Esterification without catalysis occurs for dl- alpha tocopherol, while there is also certain safety and environmental risks for the technique, because of zinc powder
It meets the substances such as water and is easy kindling, and zinc powder treatment process is complex, there is certain pollution to surrounding enviroment.
Summary of the invention
Present invention process creativeness uses weak base catalyst (nitrogen-containing basic substance) catalytic esterification, and technique is raw with dl- α
Educating phenol or dl- alpha tocopherol and dl- alpha tocopherol acetic acid ester admixture is raw material, under nitrogen-containing basic substance catalyst action,
Esterification is carried out with the mixture of acetic acid or aceticanhydride or acetic acid and aceticanhydride, esterification obtains the production of dl- alpha tocopherol acetate
Product.Specifically, the preparation method of dl- alpha tocopherol acetate of the invention specifically includes: being given birth to dl- alpha tocopherol or dl- α
Phenol and dl- alpha tocopherol acetic acid ester admixture are raw material, use nitrogen-containing basic substance for catalyst, the nitrogen-containing basic substance
Structural formula beWherein, R1、R2、R3Represent hydrogen, hydroxyl, amino, pyridyl group, by rudimentary with 1~6 carbon atom
The pyridyl group of alkyl substitution, the pyridyl group replaced by the lower alkyl amino with 1~6 carbon atom, but R1、R2、R3When different
For hydrogen, the mixture of acetic acid or aceticanhydride or acetic acid and aceticanhydride is acylating agent, and esterification obtains dl- alpha tocopherol acetate.It is excellent
Selection of land, the nitrogen-containing basic substance are selected from dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, trimethylamine, triethylamine, tripropyl amine (TPA), three
Butylamine, pyridine, N, at least one of N '-dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP).With dl- α
On the basis of the mole of tocopherol or dl- alpha tocopherol and dl- alpha tocopherol acetic acid ester admixture, the throwing of the nitrogen-containing basic substance
Doses is 0.02~0.20 mole.
Reaction process is as follows:
During technological reaction of the invention, the nitrogen-containing basic substance alkalinity as catalyst is very weak, but human hair of the present invention
The catalytic activity for being now catalyzed such esterification is stronger, so one side catalyst inventory is smaller, the temperature of esterification compared with
Low, the time is shorter；The inventory of another aspect catalyst is smaller, integrates to dl- alpha tocopherol or dl- alpha tocopherol acetate
Deng destructive very little, the extent of reaction is preferable, and yield is higher, and obtained product dl- alpha tocopherol acetate quality is higher.
During technological reaction of the invention, acylating agent is the mixture of acetic acid or aceticanhydride or acetic acid and aceticanhydride, with dl- α
On the basis of the mole of tocopherol or dl- alpha tocopherol and dl- alpha tocopherol acetic acid ester admixture, acetic acid, aceticanhydride or acetic acid and vinegar
The inventory of the mixture of acid anhydride is 1.0~10.0 moles.Wherein, when selection aceticanhydride makees acylating agent, the inventory of aceticanhydride is smaller, with
The molar ratio of dl- alpha tocopherol is preferably 1.0~2.0: 1.0 in raw material；When selection acetic acid makees acylating agent, the quantitative change that feeds intake of acetic acid
It greatly, is preferably 2.0~10.0: 1.0 with the molar ratio of dl- alpha tocopherol in raw material；During actual process, acetic acid is commonly used
With the mixture of aceticanhydride as acylating agent, the molar ratio of dl- alpha tocopherol in the inventory and raw material of the mixture of acetic acid and aceticanhydride
Preferably 1.0~10.0: 1.0, wherein acetic acid and aceticanhydride are dissolved each other in mixture with any ratio.
The present inventors have noted that using the mixture of acetic acid and aceticanhydride as acylating agent, have the advantages that it is fine, because of the ester
Change aceticanhydride and dl- alpha tocopherol in reaction and carry out esterification in addition to generating product dl- alpha tocopherol acetate, can also generate vinegar
Acid, thus acetic acid can continuous recycled, the utilization rate of acylating agent raw material greatly improves, while using acetic acid or acetic acid and vinegar
The mixture of acid anhydride is as acylating agent, since the inventory of acylating agent is larger, can play the role of a kind of solvent in the reaction, dilute
The concentration for releasing reactant is further reduced the Oxidative demage of dl- alpha tocopherol and dl- alpha tocopherol acetate, to obtain quality
Better dl- alpha tocopherol acetate product.
During technological reaction of the invention, due to there are the needs of actual production etc., raw material include dl- alpha tocopherol or
Dl- alpha tocopherol and dl- alpha tocopherol acetic acid ester admixture, wherein dl- alpha tocopherol raw material is directly raw according to dl- α in corresponding raw material
The inventory that phenol content calculates acylating agent is educated, the extent of reaction is preferable；It is dl- alpha tocopherol and dl- alpha tocopherol for practical raw material
When acetic acid ester admixture, generally other techniques are more difficult accomplishes that normal acylating agent inventory can be primarily due to correlation with fully reacting
The concentration of reactant (such as dl- alpha tocopherol and aceticanhydride) becomes smaller, and the extent of reaction reduces, then can be to avoid in present invention process
Such situation, technique of the invention use high activity nitrogen-containing basic catalyst esterification, the extent of reaction can be promoted to reach
Inventory to very high degree, acylating agent is reacted according to normal feed ratio, can also obtain qualified product, reaction yield
Higher, obtained product dl- alpha tocopherol acetate quality is preferable.
Since catalyst all has good water solubility, so after completion of the reaction, excessive acetic acid/aceticanhydride is recovered under reduced pressure,
Then directly the catalyst etc. in reaction system is extracted using a small amount of water, then will by the way of decompression or air-distillation
Residual moisture in material distills, and obtains product dl- alpha tocopherol acetate, and technical process is fairly simple, product quality compared with
It is good.
During technique of the invention is answered, the temperature of the esterification is preferably 20~120 DEG C.The esterification
Time is 1.0~5.0hr.In addition, reaction mass basically will not produce by-product or waste material in technique, finally it is used only a small amount of
Water extracting catalyst generates a small amount of waste water, and waste water can be recycled catalyst, or directly be handled as waste water, quantity
Seldom, environmental pollution etc. influences very little.
Preparation method technical process very simple of the invention, catalyst activity is stronger, and technological reaction temperature is lower,
Operational good, technological reaction degree is preferable, and yield is higher, and obtained dl- alpha tocopherol acetate product quality is higher, simultaneously
Process costs substantially reduce, and safety and the risk of environment are smaller on the whole for technique, are suitble to scale industrial production.
Detailed description of the invention
Fig. 1 shows dl- alpha tocopherol acetate sample GC maps.
Specific embodiment
The present invention is further illustrated with embodiment below, the embodiment of the present invention is merely to illustrate technical side of the invention
Case, and the non-limiting present invention.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or
It is selected according to product manual.
Embodiment 1
1.0 molar part dl- alpha tocopherol raw materials (435.0g, content 99.01%) are added in reaction flask, add acylation
1.0 molar part of agent aceticanhydride (102.5g, content 99.0%), 0.05 molar part of catalyst of triethylamine (0.26g), stir evenly, open
Begin to heat, under the conditions of temperature 45 C, react 2.0 hours, reaction is finished, and acetic acid/aceticanhydride is recovered under reduced pressure, obtains recovery of acetic acid/aceticanhydride
59.5g, recycling are finished, cooling material.
Cooling material is added 50ml water, shakes up, stand, branch vibration layer is repeated twice water extraction process, generates to room temperature
A small amount of water is recovered under reduced pressure in waste water 150ml, organic layer, obtains product dl- alpha tocopherol acetate 472.5g.
Detect dl- alpha tocopherol acetate sample, dl- alpha tocopherol content 0.06%, dl- alpha tocopherol acetate content
99.07%, obtaining technological experiment yield is 99.02% (test map is shown in annex).
Detect recovery of acetic acid/aceticanhydride, acetic acid content 96.9%, acetic anhydride level 1.2%；Triethylamine content in waste water 150ml
0.1%, COD value of waste water is smaller, can be directly as industrial wastewater discharge.
Comparing embodiment 2
1.0 molar part dl- alpha tocopherol raw materials (435.0g, content 99.01%) are added in reaction flask, add zinc powder
4.0g, 1.6 molar part of aceticanhydride (165.0g, content 99.0%), stir evenly, and are heated to 135 DEG C, react 3.0 hours, have reacted
At, acetic acid/aceticanhydride is recovered under reduced pressure, recycles and finishes, cooling material.
Cooling material is filtered to remove zinc powder, obtains product dl- alpha tocopherol acetate 460.2g to room temperature.
Detect dl- alpha tocopherol acetate sample, dl- alpha tocopherol content 0.12%, dl- alpha tocopherol acetate content
98.71%, technological experiment yield is 96.09%.
Detect recovery of acetic acid, acetic acid content 49.2%, acetic anhydride level 50.0%.
Comparison of experiment results through the foregoing embodiment is available, and embodiment 1 is using in three second of nitrogen-containing basic catalyst
Amine makees catalyst, and fcc raw material dl- alpha tocopherol and acylating agent aceticanhydride carry out esterification, and 40 DEG C of reaction temperature, the reaction time
2.0 hours, the extent of reaction was preferable, yield 99.02%, higher, while product dl- alpha tocopherol acetate quality preferably (including contains
Amount 99.07% and impurity dl- alpha tocopherol content 0.06%)；Acetate component is essentially in technique recovery of acetic acid/aceticanhydride, but still
Related esterification can be carried out to apply, it is basic without generating waste material；The amount of catalyst is seldom in technique, and a small amount of of extracting catalyst gives up
Water COD value is smaller, reaches industrial discharge standard, can be with direct emission.Integrated artistic is very simple, and temperature is lower, and operability is good
Good, esterification degree is preferable, and yield is higher, and obtained product quality is preferable, while seldom without generation waste material and generation
Waste water is suitble to scale industrial production.
Compared to embodiment 2 using under conventional zinc powder guard mode without catalytic esterification processes, raw material dl- alpha tocopherol and acyl
Agent aceticanhydride carries out esterification, 135 DEG C of reaction temperature, reacts 3.0 hours, reaction yield 96.09%, product dl- alpha tocopherol
Acetate quality is slightly poor (including content 98.71% and impurity dl- alpha tocopherol content 0.12%)；In technique recovery of acetic acid/aceticanhydride
Acetic acid content 49.2%, acetic anhydride level 50.0%, but recycled can not be carried out, generate part waste material.
Embodiment 3~8
The objective for implementation and relevant parameter of embodiment 3~8 are listed in table 1.
Table 1
Embodiment 9
1.0 molar part dl- alpha tocopherol raw materials (435.0g, content 99.01%) are added in reaction flask, add implementation
Recovery of acetic acid/aceticanhydride (59.5g, 96.9%/0.96mol of acetic acid content, 1.2%/0.007mol of acetic anhydride level) and fresh in example 1
Acetic acid (60g/1.0mol, content 99.0%), adds 0.02 molar part of catalyst DMAP (2.44g), stirs evenly, and starts
It heats, under the conditions of temperature 50 C, reacts 1.0 hours, reaction is finished, and acetic acid/aceticanhydride is recovered under reduced pressure, obtains recovery of acetic acid/aceticanhydride
76.2g, recycling are finished, cooling material.
Cooling material is added 50ml water, shakes up, stand, branch vibration layer is repeated twice water extraction process, generates to room temperature
A small amount of water is recovered under reduced pressure in waste water 150ml, organic layer, obtains product dl- alpha tocopherol acetate 471.9g.
Detect dl- alpha tocopherol acetate sample, dl- alpha tocopherol content 0.07%, dl- alpha tocopherol acetate content
98.94%, obtaining technological experiment yield is 98.76%.
Detect recovery of acetic acid/aceticanhydride, acetic acid content 76.5%；DMAP content 1.0% in waste water 150ml, COD value of waste water compared with
It is small, it can be directly as industrial wastewater discharge.
The present invention is illustrated by above embodiment, it is understood, however, that the present invention is not limited to institutes here
The particular example and embodiment of description.Purpose herein comprising these particular examples and embodiment is to help this field
In technical staff practice the present invention.Any those of skill in the art are easy to do not departing from spirit and scope of the invention
In the case of be further improved and perfect, therefore the present invention is only by the content of the claims in the present invention and the limit of range
System, intention, which covers, all to be included the alternative in the spirit and scope of the invention as defined by appendix claim and waits
Same scheme.
Claims (5)
1. a kind of method for preparing dl- alpha tocopherol acetate, the method is with dl- alpha tocopherol or dl- alpha tocopherol and dl- α
The mixture of tocopherol acetate is raw material, uses nitrogen-containing basic substance for catalyst, and the nitrogen-containing basic substance is N, N'- bis-
Carbodicyclo hexylimide, acylating agent are the mixture of acetic acid or acetic acid and aceticanhydride, and esterification obtains dl- alpha tocopherol acetate
Product.
2. method as described in claim 1, with dl- alpha tocopherol or dl- alpha tocopherol and dl- alpha tocopherol acetic acid ester admixture
On the basis of mole, the inventory of the nitrogen-containing basic substance is 0.02~0.20 mole.
3. method as described in claim 1, with dl- alpha tocopherol or dl- alpha tocopherol and dl- alpha tocopherol acetic acid ester admixture
On the basis of mole, the inventory of the mixture of acetic acid or acetic acid and aceticanhydride is 1.0~10.0 moles.
4. the method as described in claims 1 to 3 is any, the temperature of the esterification is 20~120 DEG C.
5. the method as described in claims 1 to 3 is any, the time of the esterification is 1.0~5.0hr.
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| CN103788052A (en) * | 2013-10-17 | 2014-05-14 | 安徽丰原发酵技术工程研究有限公司 | Preparation method of vitamin E acetate |
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| CN103788052A (en) * | 2013-10-17 | 2014-05-14 | 安徽丰原发酵技术工程研究有限公司 | Preparation method of vitamin E acetate |
Non-Patent Citations (2)
| Title |
|---|
| 三乙胺催化合成维生素E乙酸酯的研究;郑燕升等;《广西工学院学报》;20061231;第17卷(第3期);33-35、40 |
| 天然维生素E醋酸酯的合成;陈学兵等;《中国油脂》;20101231;第35卷(第5期);58-60 |
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