CN110156574A - A kind of preparation method of purification of alpha-ararin - Google Patents
A kind of preparation method of purification of alpha-ararin Download PDFInfo
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/32—Preparation of ethers by isomerisation
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Abstract
The present invention relates to pharmaceutical technology field, a kind of preparation method of purification of alpha-ararin.Using suitable anti-α/β-asarone mixture as raw material, including the following steps: (1) it will along anti-α/β-asarone mixture dissolve in organic solvent, stabilizer reflux water-dividing is added, solvent is evaporated off；(2) catalyst, polymerization inhibitor-antioxidant are added in the residue after solvent is evaporated off in step 1, using decompression rectification device rectifying, and continues to leak into trace nitrogen gas into rectifying material during rectification under vacuum, collects respectively and evaporate head, main distillate fraction, evaporate tail；(3) in step 2, solvent crystallization is added in the main distillate fraction steamed, and precipitate is crystallized to obtain high-purity alpha-ararin powder-product under nitrogen protection with anhydrous methanol or petroleum ether.It is proposed that preparation method of purification, alpha-ararin purity at least can reach 98% or more, β-asarone content lower than 0.62% through the invention, in addition this method is easy to operate, cost of material is low, alpha-ararin high income, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to technical field of medicine synthesis, particularly relate to a kind of preparation method of purification of alpha-ararin.
Background technique
Alpha-ararin is extracted from the volatile oil of Southern Star section plant rhizoma acori graminei earliest, have resist myocardial ischemia, relieving cough and removing sputum,
Anticonvulsion, antiulcer, anticancer, antiplatelet, a variety of pharmacological activity such as resist insane carbuncle.Clinically oneself is widely used in treatment and is breathed
The diseases such as road infection, bronchial asthma, acute and chronic cholecystitis, cholelithiasis, the big breaking-out of insane carbuncle, especially for pneumonia, branch
The treatment of the acute attack of san bronchial asthma and chronic obstructive pulmonary disease has remarkable result.But since natural resources of Chinese medicinal materials is limited and it contains
Amount is very low, complex in composition to cause to extract sterling difficulty, while being also easily mixed into the carcinogens such as yellow Chinese catalpa ether, therefore, artificial synthesized
Main source as the bulk pharmaceutical chemicals.
The primary product of artificial synthesized asarone is alpha-ararin, i.e., trans- (E) -2,4,5- trimethoxy -1- acrylic
Benzene, by-product are cis- (Z)-Alpha-Asaronum, i.e. β-asarone.β-asarone has Teratogenesis toxicity,
It can cause ovary the taking off completely of insect.The national drug standards (WS-10001- (HD-0436) -2002) provide that alpha-ararin is former
β-asarone mass content must not exceed 1% in material medicine.Therefore, artificial synthesized alpha-ararin needs to remove β-asarone or by β-
Asarone is converted into alpha-ararin.
Wang Zhicai et al. (organic chemistry, 1990,10,350-352) with 1,2,4- trimethoxy-benzene be waste 1,2,
4- trimethoxybenzaldehyde, the latter and triphenyl ethyl phosphonium bromide salt, butyl lithium prepare asarone product in tetrahydrofuran solvent,
It is about 6.5% that wherein alpha-ararin content, which is 91.3%, β-asarone content,.If prepared by replacing butyl lithium with potassium tert-butoxide
Product, β-asarone content is about 70.7%, and alpha-ararin content is about 27%.This method synthesis alpha-ararin yield compared with
It is low, and β containing by-product-asarone, need the silica gel column chromatography containing 20% silver nitrate to separate, higher cost.
The open product for being prepared wittig reaction as catalyst using palladium of Jiang Yongjun patent (publication number CN101012159A),
β-asarone in mixing α/β-asarone is converted into alpha-ararin.This method is due to using palladium catalyst and a large amount of solvent costs
It is higher, and palladium is not easy removal completely, other impurities separation is difficult；
Liu is patent (publication number CN101215226A) open α/β-asarone with wittig reaction preparation, and wherein α-is thin
Pungent brain accounts for 43%, β-asarone and accounts for 57%.In a solvent using the iodine of 0.025mol%~5mol% as catalyst, in solvent refluxing
α/β-asarone wherein will be converted into alpha-ararin by β-asarone.This method uses active iodine and a large amount of solvents, and need to extract,
The processes such as dry, complex process, higher cost, other impurities separation are difficult；
Zhu Baozhang patent (publication number CN101215226A) discloses a kind of apparatus and method of combined type purification asarone.It should
Device includes first order thin film evaporator, second level thin film evaporator, third level film filler evaporator and its auxiliary facility.It should
Method is the crude product that will be synthesized, and the raw material after being first evaporated under reduced pressure away benzene, tetrahydrofuran equal solvent uses level-one thin film evaporation, one
Grade molecular distillation and the distillation of level-one thin film filling and re-crystallization step, packet the include level-one degassing process, are removed with thin film evaporator
Solvent, second level molecular distillation remove β-asarone, obtain alpha-ararin, it is thin that the purification of third level thin film filling distiller steams β-
Pungent brain, then the high purity product for extracting and recrystallizing through ethyl alcohol.This method apparatus and process is complicated, cannot convert β-asarone to
Unavoidably there is asarone and polymerization, gel reaction occur in alpha-ararin, distillation process bottom, product recovery rate is not high to ask
Topic.
It is still had been reported that about substituted ethylene base cis-trans isomerization reaction document.Heather A B et al. proposes (Heather
A B,Samuel I S.Synthesis of stilbene carboxylic acids as scaffolds for
Calcium sensors [J] .Chem.Commum., 2005,4845-4847.) high temperature and strong alkaline condition be easy to make be conjugated more
Cis-trans isomerization occurs for the double bond in system.
Liu Xiyang (Liu Xiyang reacts the synthesis Hunan hexichol ene-type retinoids [D]: Hunan University without phosphine palladium chtalyst Heck,
It 2008.) will be instead, along 1,2- diphenyl substituted ethylene type retinoids (E/Z=56:44) in tetrahydrofuran water using lithium hydroxide
It is reacted in solution, discovery is there are ethylene linkage isomerization reaction, and transconfiguration component ratio increases (E/Z >=98:2) in product.
The reaction of document report substituted ethylene base cis-trans isomerization has different mechanism.Wang Nuanqing (Wang Nuanqing β substituted benzene
The Hunan theoretical research [D] of vinyl isomerization mechanism: University Of Xiangtan, 2010.) use HF Ab initio and DFT method pair
The heat of styrene, 1- methyl -2- phenylethylene, 1- methoxyl group -2- phenylethylene and 1- [1,3] oxepane -2- phenylethylene
Isomerization mechanism is studied.And analysis is compared to reaction from structure, energy and charge etc., it was therefore concluded that:
The transition state of an ethylene double bond singly-bound is passed through in cis-trans isomerism reaction；The property of olefin substituent has the activation energy of reaction
Very big influence, wherein methyl influences maximum, because it can carry more charge, is conducive to transition state and stablizes, reduce activation energy；1-
The energy barrier of methyl -2- phenylethylene isomerization is minimum, is 48.2kcal mol-1, therefore is easiest to carry out isomerization reaction, and
The styrene of unsubstituted is then up to 154.5kcal mol-1, and temperature-sensitive isomerization reaction is difficult.
Alpha-ararin fusing point is lower (60~61 DEG C), and recrystallization speed is relatively slow (3~5 days), and effect is poor, exists in mother liquor
Large-tonnage product recycling is difficult；Boiling point is higher (296 DEG C), and the reactions such as polymerization, oxidation easily occur for conventional distil-lation, and yield is caused to reduce,
It is easy bumping, coking glues wall and is difficult to clear up.It is of the invention for above-mentioned the problem of alpha-ararin preparation is with purification process
Using α/β-asarone as raw material, the mode of isomerization reaction progress synchronous with rectifying is taken, completes the conversion of β-asarone and α-
The reaction and purifying of asarone overcome above-mentioned β-asarone conversion reaction and many and diverse disadvantage of separating technology, it is thin to solve α-
Pungent brain is easy to happen the problems such as polymerization, coking, bumping, viscous wall in distillation process, realizes the conversion of by-product β-asarone
Using and product alpha-ararin impurity elimination and purification, improve product utilization rate.With easy to operate, cost of material is low, α-
The advantage of asarone high income, purity is high, it is easy to accomplish industrialized production.
Summary of the invention
The present invention proposes the preparation and its method of purification of a kind of alpha-ararin, overcomes deficiency in the prior art, provides
A kind of easy to operate, energy conservation and environmental protection, green high-efficient, low in cost, solvent usage amount be small and the recyclable α-asarum reused
Brain preparation process.
The technical scheme of the present invention is realized as follows:
A kind of preparation and its method of purification of alpha-ararin, using suitable anti-α/β-asarone mixture as raw material, including it is following
Several steps:
(1) it will be dissolved in organic solvent along anti-α/β-asarone mixture, stabilizer reflux water-dividing is added, solvent is evaporated off；
(2) catalyst, polymerization inhibitor-antioxidant are added in the residue after solvent is evaporated off in step 1, uses rectification under vacuum
Device rectifying, and during rectification under vacuum continue trace nitrogen gas is leaked into rectifying material, respectively collect evaporate head, main distillate fraction,
Evaporate tail；
(3) in step 2, solvent crystallization is added in the main distillate fraction steamed, and precipitate uses anhydrous methanol or stone under nitrogen protection
Oily ether crystallizes to obtain high-purity alpha-ararin powder-product.
Preferably, in step (1), in the suitable anti-α/β-asarone mixture β-asarone mass fraction be 1%~
40%.
Preferably, in step (1), the organic solvent is dichloroethanes, trichloroethanes, one in benzene,toluene,xylene
Kind.
Preferably, in step (1), the stabilizer is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, carbonic acid
One or more combinations in potassium, saleratus, additional amount are the 0.2%~2.0% of material quality.
Preferably, in step (2), the catalyst is one of sodium hydroxide, potassium hydroxide or two kinds of combinations, is added
Amount is the 1.0%~10% of material quality.
Preferably, in step (2), the polymerization inhibitor-antioxidant be one of zinc powder, copper powder, glass putty or multiple combinations,
Additional amount is the 0.1%~5.0% of material quality.
Preferably, in step (2), the vacuum distillation apparatus is packed tower decompression rectification device, and filler is wire mesh
One of filler, ceramic packing, conjugate ring or Pall ring, the number of plates are 4~15, and reflux ratio is 1.2~2.
Preferably, in step (2), the head that evaporates of collection is the 4%~8% of material quality, collects the condition of main distillate fraction
For pressure: 1kPa~15kPa, temperature: 150 DEG C~195 DEG C；That collects evaporates 1%~5% that tail is material quality.
Preferably, in step (3), the solvent that main distillate fraction is added is one of methanol, ethyl alcohol, petroleum ether or a variety of
Combination, additional amount are the 2%-10% of main distillate fraction quality.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention realizes following production technology process scheme: a kind of preparation and its method of purification of alpha-ararin, with suitable
Anti- α/β-asarone mixture is raw material, which is characterized in that including the following steps:
(1) it will be dissolved in organic solvent along anti-α/β-asarone mixture, stabilizer reflux water-dividing is added, solvent is evaporated off；
(2) catalyst, polymerization inhibitor-antioxidant are added in the residue after solvent is evaporated off in step 1, uses rectification under vacuum
Device rectifying, and during rectification under vacuum continue trace nitrogen gas is leaked into rectifying material, respectively collect evaporate head, main distillate fraction,
Evaporate tail；
(3) in step 2, solvent crystallization is added in the main distillate fraction steamed, and precipitate uses anhydrous methanol or stone under nitrogen protection
Oily ether crystallizes to obtain high-purity alpha-ararin powder-product.
Preferably, in step (1), in the suitable anti-α/β-asarone mixture β-asarone mass fraction be 1%~
40%.It include artificial synthesized asarone, recrystallization mother liquor recycling asarone, asarone rectifying receipts along anti-α/β-asarone mixture
Evaporating for collection and evaporates tail at head.
Preferably, in step (1), the organic solvent is dichloroethanes, trichloroethanes, one in benzene,toluene,xylene
Kind.Because benzene, toluene effect are more preferable, preferably benzene or toluene, solvent adding amount is that per kilogram raw material is added 1~4 liter of solvent.
Preferably, in step (1), the stabilizer is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, carbonic acid
One or more combinations, preferably sodium hydroxide or potassium hydroxide in potassium, saleratus, additional amount be material quality 0.2%~
2.0%.
Preferably, in step (2), the catalyst is one of sodium hydroxide, potassium hydroxide or two kinds of combinations, is added
Amount is the 1.0%~10% of material quality.
Preferably, in step (2), the polymerization inhibitor-antioxidant be one of zinc powder, copper powder, glass putty or multiple combinations,
Due to zinc powder cheaper, preferably zinc powder, additional amount is the 0.1%~5.0% of material quality.
Preferably, in step (2), the vacuum distillation apparatus is packed tower decompression rectification device, and filler is wire mesh
One of filler, ceramic packing, conjugate ring or Pall ring, the number of plates are 4~15, and reflux ratio is 1.2~2.Due to wire
Net effect is more preferable, preferably wire mesh packing.
Preferably, in step (2), the head that evaporates of collection is the 4%~8% of material quality, collects the condition of main distillate fraction
For pressure: 1kPa~15kPa, temperature: 150 DEG C~195 DEG C；That collects evaporates 1%~5% that tail is material quality.In addition, leaking into
Trace nitrogen gas is imported with capillary, is advisable with not generating continuous air bubbles state flow.
Preferably, in step (3), the solvent that main distillate fraction is added is one of methanol, ethyl alcohol, petroleum ether or a variety of
Combination, since methanol effect is more preferable, preferably methanol, additional amount are main distillate fraction quality
2%-10%.
It is the reaction process formula that β of the present invention-asarone conversion prepares alpha-ararin below:
The process that cis- (β -) asarone is converted into trans- (α -) asarone is similar to 1- methyl -2- phenylethylene isomerization
Mechanism, conjugated double bond fracture generate the transition state A that double bond becomes singly-bound, and the transition state is double because the presence of terminal methyl is more stable
Key fracture activation energy is lower, is also easy to be changed into transition state B, to be conducive to isomerization reaction.
Isomerization process has very high chemical activity, is easy to happen poly- due to passing through singly-bound transition state, this state
The side reactions such as conjunction, oxidation, to prevent this kind of side reaction from occurring, polymerization inhibitor-antioxidant is added in this patent, and uniformly leaks into nitrogen and give
It is synchronous to realize reaction and isolate and purify process with protection and power-assisted rectifying.
Specific embodiment:
Each step of the invention is described in detail below with reference to specific embodiment, but the present invention is not limited to following
Embodiment.
Alpha-ararin and β-asarone assay refer to second annex V E gas chromatography of Chinese Pharmacopoeia version in 2000
(GC)。
Embodiment 1
It takes with α/β-asarone of 2,4,5- trimethoxy -1- phenylpropyl alcohol dehydration of alcohols preparation (GC measures E/Z=94.3/5.7)
750mL benzene is added into 2000mL round-bottomed flask in 750g, and sodium hydroxide 1.5g is added, and temperature rising reflux divides water 1h, steams solvent,
Sodium hydroxide 75g, zinc powder 19.5g is added, is evaporated under reduced pressure with the rectifier unit (number of plates 6) for being filled with wire mesh packing, slowly
Nitrogen is leaked into drag, controls reflux ratio 2.0, collection evaporates about 30 grams of head, changes receiving bottle and collects 173-175 DEG C of main distillate fraction
(11.5kPa), speed to be distilled are obviously reduced, and change receiving bottle collection and evaporate about 7.5 grams of tail.75mL methanol, room is added in main distillate fraction
Temperature, which is placed, is precipitated solid, and nitrogen protection and the lower recrystallizing methanol of stirring obtain white crystals 594.8g, yield 79.3%, fusing point
60~61 DEG C, it is 0.48% that GC analysis alpha-ararin content, which is 99.0%, β-asarone content,.
Embodiment 2
It takes with α/β-asarone of 2,4,5- trimethoxy -1- phenylpropyl alcohol dehydration of alcohols preparation (GC measures E/Z=92.6/7.3)
960mL benzene is added into 2000mL round-bottomed flask in 240g, and potassium hydroxide 4.8g is added, and temperature rising reflux divides water 1h, steams solvent,
Sodium hydroxide 13.2g, zinc powder 12g is added, is evaporated under reduced pressure with the rectifier unit (number of plates 6) for being filled with wire mesh packing, slowly
Nitrogen is leaked into drag, controls reflux ratio 1.2, collection evaporates about 14.4 grams of head, changes receiving bottle 192-195 DEG C of master of collection and evaporates
Divide (15kPa), speed to be distilled is obviously reduced, and changes receiving bottle collection and evaporates about 7.2 grams of tail.14.4mL methanol is added in main distillate fraction,
It is placed at room temperature for precipitation solid, nitrogen protection and the lower recrystallizing methanol of stirring, obtains white crystals 177g, yield 72.3%, fusing point
60~61 DEG C, it is 0.48% that GC analysis alpha-ararin content, which is 99.0%, β-asarone content,.
Embodiment 3
Product recrystallizing methanol disposing mother liquor product α/β-asarone in Example 1 (GC measures E/Z=90.5/9.5)
1125mL toluene is added into 2000mL round-bottomed flask in 450g, and potassium hydroxide 5g is added, and temperature rising reflux divides water 1h, steams solvent,
Potassium hydroxide 4.5g, glass putty 0.45g is added, is evaporated under reduced pressure with the rectifier unit (number of plates 6) for being filled with wire mesh packing, slowly
Nitrogen is leaked into drag, controls reflux ratio 1.4, collection evaporates about 36 grams of head, changes receiving bottle and collects 150-153 DEG C of main distillate fraction
(1kPa), speed to be distilled are obviously reduced, and change receiving bottle collection and evaporate about 23 grams of tail.9mL methanol is added in main distillate fraction, is placed at room temperature for
It is precipitated solid, nitrogen protection and stirs lower recrystallizing methanol, obtain white crystals 335g, yield 74.4%, 60~61 DEG C of fusing point,
It is 0.56% that GC analysis alpha-ararin content, which is 98.8%, β-asarone content,.
Embodiment 4
Product recrystallizing methanol disposing mother liquor product α/β-asarone in Example 3 (GC measures E/Z=88.2/11.8)
400mL toluene is added into 2000mL round-bottomed flask in 400g, and sodium hydroxide 0.8g is added, and temperature rising reflux divides water 1h, steams molten
Potassium hydroxide 22g, copper powder 20g is added in agent, is evaporated under reduced pressure with the rectifier unit (number of plates 6) for being filled with wire mesh packing, slowly
Nitrogen is leaked into drag, controls reflux ratio 1.6, collection evaporates about 24 grams of head, changes receiving bottle and collects 175-177 DEG C of main distillate fraction
(11.5kPa), speed to be distilled are obviously reduced, and change receiving bottle collection and evaporate about 18 grams of tail.24mL methanol, room temperature is added in main distillate fraction
It places and solid is precipitated, nitrogen protection and the lower recrystallizing methanol of stirring obtain white crystals 288g, yield 72%, fusing point 60~61
DEG C, it is 0.56% that GC analysis alpha-ararin content, which is 98.8%, β-asarone content,.
Embodiment 5
Head is evaporated in Example 1, and 360g is extremely with tail melange α/β-asarone (GC measures E/Z=86.5/13.5) is evaporated
In 2000mL round-bottomed flask, 720mL benzene is added, sodium hydroxide 4g is added, temperature rising reflux divides water 1h, steams solvent, and hydrogen-oxygen is added
Change potassium 3.6g, zinc powder 9.5g, is evaporated under reduced pressure with the rectifier unit (number of plates 6) for being filled with wire mesh packing, slowly leaks into nitrogen
To drag, reflux ratio 1.2 is controlled, collection evaporates about 28 grams of head, changes receiving bottle and collects 175-177 DEG C of main distillate fraction
(11.5kPa), speed to be distilled are obviously reduced, and change receiving bottle collection and evaporate about 18 grams of tail.21mL ethyl alcohol, room temperature is added in main distillate fraction
It places and solid is precipitated, nitrogen protection and the lower recrystallizing methanol of stirring obtain white crystals 277.6g, yield 77.1%, fusing point 60
~61 DEG C, it is 0.62% that GC analysis alpha-ararin content, which is 98.5%, β-asarone content,.
Embodiment 6
Head is evaporated in Example 5, and 200g is extremely with tail melange α/β-asarone (GC measures E/Z=85.2/14.8) is evaporated
In 2000mL round-bottomed flask, 800mL benzene is added, sodium hydroxide 0.4g is added, temperature rising reflux divides water 1h, steams solvent, and hydrogen is added
Sodium oxide molybdena 5.2g, zinc powder 9.5g are evaporated under reduced pressure with the rectifier unit (number of plates 6) for being filled with wire mesh packing, slowly leak into nitrogen
Gas controls reflux ratio 1.2, collection evaporates about 8 grams of head, changes receiving bottle and collects 175-177 DEG C of main distillate fraction to drag
(11.5kPa), speed to be distilled are obviously reduced, and change receiving bottle collection and evaporate about 6 grams of tail.20mL methanol, room temperature is added in main distillate fraction
It places and solid is precipitated, nitrogen protection and stir lower recrystallizing methanol, obtain white crystals 149g, yield 74.5%, fusing point 60~
61 DEG C, it is 0.62% that GC analysis alpha-ararin content, which is 98.5%, β-asarone content,.
In conclusion the preparation method of purification proposed through the invention, alpha-ararin purity at least can reach 98% with
On, in addition, this method is easy to operate, cost of material is low, alpha-ararin high income；And in this method, it is thin to convert incomplete β-
Pungent brain can continue to serve as raw material conversion in conversion next time, and then reduce wastage of material, it is easy to accomplish industrialized production.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. the preparation method of purification of a kind of alpha-ararin, using suitable anti-α/β-asarone mixture as raw material, which is characterized in that including
Following steps:
(1) it will be dissolved in organic solvent along anti-α/β-asarone mixture, stabilizer reflux water-dividing is added, solvent is evaporated off；
(2) catalyst, polymerization inhibitor-antioxidant are added in the residue after solvent is evaporated off in step 1, uses decompression rectification device
Rectifying, and continue to leak into trace nitrogen gas into rectifying material during rectification under vacuum, it collects respectively and evaporates head, main distillate fraction, evaporates tail；
(3) in step 2, solvent crystallization is added in the main distillate fraction steamed, and precipitate uses anhydrous methanol or petroleum ether under nitrogen protection
Crystallization obtains high-purity alpha-ararin powder-product.
2. preparation method of purification according to claim 1, which is characterized in that in step (1), the suitable anti-α/β-asarone is mixed
Closing β-asarone mass fraction in object is 1%~40%.
3. preparation method of purification according to claim 1, which is characterized in that in step (1), the organic solvent is two chloroethenes
One of alkane, trichloroethanes, benzene,toluene,xylene.
4. preparation method of purification according to claim 1, which is characterized in that in step (1), the stabilizer is hydroxide
Sodium, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, one or more combinations in saleratus, additional amount is material quality
0.2%~2.0%.
5. preparation method of purification according to claim 1, which is characterized in that in step (2), the catalyst is hydroxide
One of sodium, potassium hydroxide or two kinds of combinations, additional amount is the 1.0%~10% of material quality.
6. preparation method of purification according to claim 1, which is characterized in that in step (2), the polymerization inhibitor-antioxidant is
One of zinc powder, copper powder, glass putty or multiple combinations, additional amount are the 0.1%~5.0% of material quality.
7. preparation method of purification according to claim 1, which is characterized in that in step (2), the vacuum distillation apparatus is to fill out
Expect that tower decompression rectification device, filler are one of wire mesh packing, ceramic packing, conjugate ring or Pall ring, the number of plates 4
~15, reflux ratio is 1.2~2.
8. preparation method of purification according to claim 1, which is characterized in that in step (2), the head that evaporates of collection is raw material
The 4%~8% of quality, the condition for collecting main distillate fraction is pressure: 1kPa~15kPa, temperature: 150 DEG C~195 DEG C；That collects evaporates
Tail is the 1%~5% of material quality.
9. preparation method of purification according to claim 8, which is characterized in that in step (3), the solvent of main distillate fraction addition
For one of methanol, ethyl alcohol, petroleum ether or multiple combinations, additional amount is the 2%-10% of main distillate fraction quality.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215226A (en) * | 2008-01-02 | 2008-07-09 | 湖南师范大学 | Method for synthesizing alpha-asarone |
| CN103254043A (en) * | 2013-05-22 | 2013-08-21 | 华南理工大学 | Combined type asarin purification device and method |
| CN103755533A (en) * | 2013-12-26 | 2014-04-30 | 北京林业大学 | Method for synthesizing anethole by taking estragole oil as raw material |
| CN104311399A (en) * | 2014-10-09 | 2015-01-28 | 广西壮族自治区林业科学研究院 | Method for converting estragole into trans-anethole |
| CN105111051A (en) * | 2015-09-07 | 2015-12-02 | 广西亿康药业股份有限公司 | Green solvent for alpha-asarin synthesis and application method thereof |
-
2019
- 2019-07-03 CN CN201910594149.XA patent/CN110156574A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215226A (en) * | 2008-01-02 | 2008-07-09 | 湖南师范大学 | Method for synthesizing alpha-asarone |
| CN103254043A (en) * | 2013-05-22 | 2013-08-21 | 华南理工大学 | Combined type asarin purification device and method |
| CN103755533A (en) * | 2013-12-26 | 2014-04-30 | 北京林业大学 | Method for synthesizing anethole by taking estragole oil as raw material |
| CN104311399A (en) * | 2014-10-09 | 2015-01-28 | 广西壮族自治区林业科学研究院 | Method for converting estragole into trans-anethole |
| CN105111051A (en) * | 2015-09-07 | 2015-12-02 | 广西亿康药业股份有限公司 | Green solvent for alpha-asarin synthesis and application method thereof |
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