CN103755533A - Method for synthesizing anethole by taking estragole oil as raw material - Google Patents
Method for synthesizing anethole by taking estragole oil as raw material Download PDFInfo
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- CN103755533A CN103755533A CN201310737086.1A CN201310737086A CN103755533A CN 103755533 A CN103755533 A CN 103755533A CN 201310737086 A CN201310737086 A CN 201310737086A CN 103755533 A CN103755533 A CN 103755533A
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- anethole
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- estragole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing anethole by taking estragole oil as a raw material. The estragole oil is subjected to isomerization reaction in the presence of a basic catalyst, and is frozen, crystallized and separated, so as to obtain trans-anethole. The method is cheap in raw material and is simple and safe; meanwhile, the reuse value of a by-product is achieved, and the purity of the obtained anethole can be up to over 96% by optimization on rectification and extraction conditions, so that the method is applicable to industrial production.
Description
Technical field
The present invention relates to a kind of method of synthesizing trans-anethole take estragole oil as raw material, belong to spices manufacture field.
Background technology
Trans-anethole, also claims isoesdragol, methyl allylphenol etc., is divided into suitable, trans isomer, is star anise main body of oil.Cis trans-anethole, with pungent irritating smell and there is certain toxicity, is therefore limited a small amount of use.
Trans trans-anethole confirms can be used as seasonings, the perfuming agent of food through FEMA (numbering 2086), be widely used in foodstuffs industry, by human body, is taken in a large number, also can be used as masking agent and is widely used in daily necessities industry and other industry.The structural formula of trans trans-anethole is as follows:
In prior art, natural trans-anethole is mainly produced from method by star aniseed oil list, as disclosed in patents such as CN102491884A, CN1055174A and CN101898941A from star aniseed oil single method from high purity trans-anethole, these class methods can effectively separate the trans-anethole in star aniseed oil, but the estragole containing in star aniseed oil can not effectively utilize; And synthetic trans-anethole is mainly take methyl-phenoxide as raw material, with after propanoic derivatives (as the third aceticanhydride, propionyl chloride etc.) acidylate, then obtain through reducing, dewater, refining, as CN103058835A.But this technological process is longer, total recovery approximately 60%.
Estragole oil is star aniseed oil list from producing in trans-anethole process, the by product going out by rectifying separation, and wherein estragole content 78-90% not etc., does not separately contain the compositions such as Terpineol 350, trans-anethole conventionally.How cheap estragole being converted into the product that value is higher, improving the comprehensive utilization ratio of star aniseed oil, is one of spices enterprise problem demanding prompt solution.
Summary of the invention
The problem of making a low multiple use in order to solve star aniseed oil, the present invention, take estragole oil as raw material, obtains the synthetic method of the trans-anethole of a kind of low cost, high yield, and its trans trans-anethole purity is up to more than 96%.
To achieve these goals, the present invention adopts following technical scheme:
A method for synthetic trans-anethole take estragole oil as raw material, the isomerization reaction under basic catalyst effect of estragole oil, freezing and crystallizing, separates, and obtains trans trans-anethole.
The concrete steps of above-mentioned synthetic method are:
1), under the effect of basic catalyst, estragole oil is isomerization reaction 0.5-3h at 140-215 ℃ of temperature;
2) step 1) products therefrom is first cooled to 50-80 ℃, stratification after washing, by gained oil reservoir freezing and crystallizing, fragmentation, separates, and obtains trans-anethole crude product.
Wherein, in step 1), described basic catalyst is KOH/Al
2o
3, in the combination such as sodium amide, KOH/NaOH, KOH/ polyoxyethylene glycol, KOH/NaOH/ polyoxyethylene glycol one or more; Described basic catalyst consumption is the 3-10% of estragole oil quality.
In step 2) in, described freezing and crystallizing condition: temperature 0-5 ℃, time 5-24h.
The present invention is take the byproduct estragole oil that produces in natural trans-anethole production process as raw material, isoparaffin synthesis trans-anethole under basic catalyst effect, and raw material is cheap, and method is simple, and safety realizes byproduct recycle value simultaneously, is applicable to very much suitability for industrialized production.
In order to obtain the trans-anethole that purity is higher, the present invention is also to the further rectification and purification of trans-anethole crude product.Be specially trans-anethole crude product at vacuum tightness 99.4KPa-99.8KPa, carry out rectifying separation under reflux ratio 5-8:1 condition, the cut between collecting 120-124 ℃, obtains high purity trans-anethole.
The present invention, by the optimization to rectification and purification condition, effectively improves the comprehensive utilization ratio of star aniseed oil, and gained trans-anethole purity reaches more than 96%, meets product standard, is applicable to suitability for industrialized production.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
6gKOH, 3gNaOH are mixed with to KOH/NaOH basic catalyst.To being equipped with in the stainless steel triangular flask of 120g estragole oil (estragole GC content 78.2%), add the catalyzer making, under stirring, refluxing, be warmed up to rapidly approximately 210 ℃, and sustained reaction 2.5h.React complete, be cooled to 70 ℃, add hot wash 2 times, stratification, is placed in refrigerator by gained oil reservoir, carries out freezing and crystallizing, crystallization time 20h at 2 ℃.By the crystal fracture obtaining, use whizzer to separate, obtain trans-anethole crude product 75.7g.
The trans-anethole crude product obtaining, at vacuum tightness 99.4KPa, is carried out to rectifying separation under reflux ratio 6:1 condition, the cut between collecting 123 ℃ obtains the finished product 68.4g, relative efficiency estragole yield 72.9%, trans-anethole content 99.6%, wherein trans trans-anethole content 96.9%.
Embodiment 2
Get 10gKOH and 15g cetomacrogol 1000 in stainless steel flask, use electric mantle be heated to melt completely and be warmed up to 210 ℃, with dripping 154g estragole oil (estragole GC content 78.2%) in backward flask, reflux and stir down reaction 1.5h left and right.React complete, be cooled to 60 ℃, add hot wash 2 times, stratification, is placed in refrigerator by gained oil reservoir, at 2 ℃ of temperature, refrigerates crystallization 20h.The crystal obtaining is added to-5 ℃ of icy salt solution 100ml fragmentations, use whizzer to separate, obtain trans-anethole crude product 115.1g.
The trans-anethole crude product obtaining, at vacuum tightness 99.8KPa, is carried out to rectifying separation under reflux ratio 7:1 condition, the cut between collecting 124 ℃ obtains the finished product 104.4g, relative efficiency estragole yield 86.7%, trans-anethole content 99.6%, trans trans-anethole content 98.1%.
Embodiment 3
Get KOH10g, cetomacrogol 1000 20g in stainless steel there-necked flask, use electric mantle be heated to melt completely and be warmed up to 150 ℃, with dripping 154g estragole oil (estragole GC content 78.2%) in backward flask, reflux and stir down reaction 1h.React complete, be cooled to 80 ℃, add hot wash 2 times, stratification, is placed in refrigerator by gained oil reservoir, at 2 ℃ of temperature, refrigerates crystallization 24h.The crystal obtaining is added to-5 ℃ of icy salt solution 100ml fragmentations, use whizzer to separate, obtain trans-anethole crude product 106.8g.
The trans-anethole crude product obtaining, at vacuum tightness 99.4KPa, is carried out to rectifying separation under reflux ratio 6:1 condition, the cut between collecting 120 ℃ obtains the finished product 97.8g, relative efficiency estragole yield 83.6%, trans-anethole content 99.5%, trans trans-anethole content 97.7%.
Embodiment 4
Get 120g estragole oil (estragole GC content 78.2%) and be added in stainless steel there-necked flask, be heated with stirring to backflow, with adding sodium amide 4.5g in backward flask, continue back flow reaction 1h.React complete, be cooled to 50 ℃, add hot wash 2 times, stratification, is placed in refrigerator by gained oil reservoir, at 2 ℃ of temperature, refrigerates crystallization 18h.The crystal obtaining is added to-5 ℃ of icy salt solution 100ml fragmentations, use whizzer to separate, obtain trans-anethole crude product 84.6g.
The trans-anethole crude product obtaining, at vacuum tightness 99.4KPa, is carried out to rectifying separation under reflux ratio 7:1 condition, the cut between collecting 124 ℃ obtains the finished product 69.9g, relative efficiency estragole yield 74.5%, trans-anethole content 99.6%, trans trans-anethole content 96.9%.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (6)
1. a method for synthetic trans-anethole take estragole oil as raw material, is characterized in that, the isomerization reaction under basic catalyst effect of estragole oil, and freezing and crystallizing, separates, and obtains trans trans-anethole.
2. method according to claim 1, is characterized in that, concrete steps are:
1), under the effect of basic catalyst, estragole oil is isomerization reaction 0.5-3h at 140-215 ℃ of temperature;
2) step 1) products therefrom is first cooled to 50-80 ℃, stratification after washing,
By gained oil reservoir freezing and crystallizing, fragmentation, separates, and obtains trans-anethole crude product.
3. method according to claim 2, is characterized in that, in step 1), described basic catalyst is KOH/Al
2o
3, in the combination such as sodium amide, KOH/NaOH, KOH/ polyoxyethylene glycol, KOH/NaOH/ polyoxyethylene glycol one or more.
4. method according to claim 2, is characterized in that, in step 1), described basic catalyst consumption is the 3-10% of estragole oil quality.
5. method according to claim 2, is characterized in that, in step 2) in, described freezing and crystallizing condition: temperature 0-5 ℃, time 5-24h.
6. method according to claim 2, is characterized in that, to step 2) the further rectification and purification of gained trans-anethole crude product, be specially trans-anethole crude product at vacuum tightness 99.4KPa-99.8Kpa, under reflux ratio 5-8:1 condition, carry out rectifying separation, the cut between collecting 120-124 ℃, obtains trans-anethole.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310737086.1A CN103755533B (en) | 2013-12-26 | 2013-12-26 | Method for synthesizing anethole by taking estragole oil as raw material |
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| CN201310737086.1A CN103755533B (en) | 2013-12-26 | 2013-12-26 | Method for synthesizing anethole by taking estragole oil as raw material |
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| CN103755533A true CN103755533A (en) | 2014-04-30 |
| CN103755533B CN103755533B (en) | 2015-05-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105152877A (en) * | 2015-09-08 | 2015-12-16 | 广西中烟工业有限责任公司 | Preparation method for estragole and application of estragole |
| CN106350223A (en) * | 2016-08-26 | 2017-01-25 | 江西依思特香料有限公司 | Preparation method of estragole |
| CN110156574A (en) * | 2019-07-03 | 2019-08-23 | 承德石油高等专科学校 | A kind of preparation method of purification of alpha-ararin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2268001A1 (en) * | 1974-04-19 | 1975-11-14 | Haarmann & Reimer Gmbh | |
| CN101898941A (en) * | 2010-07-27 | 2010-12-01 | 中山大学 | Method for purifying trans-anethole |
-
2013
- 2013-12-26 CN CN201310737086.1A patent/CN103755533B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2268001A1 (en) * | 1974-04-19 | 1975-11-14 | Haarmann & Reimer Gmbh | |
| CN101898941A (en) * | 2010-07-27 | 2010-12-01 | 中山大学 | Method for purifying trans-anethole |
Non-Patent Citations (1)
| Title |
|---|
| 曹婷婷等: "1-烯丙基-4-甲氧基苯碱性异构研究", 《现代化工》, vol. 31, June 2011 (2011-06-01) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105152877A (en) * | 2015-09-08 | 2015-12-16 | 广西中烟工业有限责任公司 | Preparation method for estragole and application of estragole |
| CN106350223A (en) * | 2016-08-26 | 2017-01-25 | 江西依思特香料有限公司 | Preparation method of estragole |
| CN110156574A (en) * | 2019-07-03 | 2019-08-23 | 承德石油高等专科学校 | A kind of preparation method of purification of alpha-ararin |
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| CN103755533B (en) | 2015-05-27 |
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