CN107216359A - A kind of synthetic method of β ursin - Google Patents
A kind of synthetic method of β ursin Download PDFInfo
- Publication number
- CN107216359A CN107216359A CN201710605643.2A CN201710605643A CN107216359A CN 107216359 A CN107216359 A CN 107216359A CN 201710605643 A CN201710605643 A CN 201710605643A CN 107216359 A CN107216359 A CN 107216359A
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- CN
- China
- Prior art keywords
- ursin
- synthetic method
- acetyl
- molar ratio
- deacetylation
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
- C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
Abstract
The invention discloses a kind of synthetic method of β ursin, belong to the synthesis field of daily use chemicals additive.The synthetic method that a kind of yield may be up to 81 90% is aimed to provide, this method by four acetyl ursin acetylations, again by its product deacetylation by obtaining；Wherein, four described acetyl ursin are five acetyl glucose and hydroquinones and its obtained by derivative reacts under ionic liquid.The present invention can be used for the synthesis of β ursin in chemical product.
Description
Technical field
The invention belongs to the synthesis field of daily use chemicals additive, especially a kind of synthetic method of β-ursin.
Background technology
The source of β-ursin will can substantially be divided into extracted form natural plant, Plant Tissue Breeding, enzyme transforming process and chemistry and close
Prepared into four kinds of methods, first three methods there is no method to industrialize by the restriction of the factors such as low yield, complex operation, cost height
Production, existing market β-ursin is all from chemical synthesis.
The method of chemical synthesis β-ursin mainly has：Direct reaction method, the sugared method of acetylation and acetyl halide glucose method.It is directly anti-
Answer method most simple, in the presence of acidic catalyst, sugar and hydroquinones thermal condensation altogether, product is the mixing of glucosides isomers
Thing, this method is not suitable for preparing disaccharides, disaccharides facile hydrolysis in acid condition.Acidic catalyst can be hydrogen chloride, cation
Resin.Hydrogen chloride is as catalyst, it is necessary to which silver carbonate dechlorinates.Resin cation may filter that gained filtrate exists after completion of the reaction
Glucosides is made by Steppecd crystallization at room temperature.
At present, most commonly used application be with five acetyl glucose and hydroquinones lewis acid such as p-methyl benzenesulfonic acid,
Reacted under the catalysis of BFEE etc..The β of synthesis-ursin total recovery is no more than 60%.
The content of the invention
For above-mentioned deficiency, the present invention is intended to provide a kind of synthetic method of β-ursin, this method can improve yield
To 81-90%.
In order to realize above-mentioned technique effect, the technical scheme that the present invention is provided is such：A kind of synthesis of β-ursin
Method, described ursin by four acetyl ursin acetylations, again by its product deacetylation by obtaining；
Wherein, four described acetyl ursin by by five acetyl glucose and hydroquinones and its derivative in ionic liquid
Gained is reacted under body.
Wherein, the molar ratio of four described acetyl ursin and acetylizing agent, deacetylated base is 1:1-2:2-10.
Wherein, the molar ratio of four described acetyl ursin and acetylizing agent, deacetylated base is 1:1.1:1.5.
Wherein, the molar ratio of described five acetyl glucose and benzenediol and its derivative is 1:1-2.
Wherein, the molar ratio of described five acetyl glucose and benzenediol and its derivative is 1:1.5.
Wherein, described ionic liquid is the combination of one or both of ferric trichloride, chlorinated butyl methylimidazole.
Wherein, the acetylizing agent used in the acetylation is the one or more in chloroacetic chloride, acetic anhydride and glacial acetic acid.
Wherein, the acetylizing agent used in the acetylation is acetic anhydride.
Wherein, the reaction temperature of the acetylation is 50-100 DEG C, and the reaction time is 1-3 hours.
Wherein, the reaction temperature of the acetylation is 60-70 DEG C, and the reaction time is 1.5 hours.
Wherein, the reagent used in described deacetylation is aqueous ammonium chloride solution.
Wherein, the reaction temperature of described deacetylation is 60-80 DEG C, and the reaction time is 1-3 hours.
Wherein, the reaction temperature of described deacetylation is 70 DEG C, and the reaction time is 2 hours.
The present invention can improve the yield of β-ursin to 81-90% compared with conventional method.
Embodiment
With reference to embodiment, the claim to the present invention is described in further detail, but is not constituted pair
Any limitation of the present invention, any limited number of time modification made in the claims in the present invention protection domain, still the present invention's
In claims.
Embodiment 1
Four acetyl ursin 44g (0.1mol) are put into the three-necked flask with stirring, 200ml toluene, stirring is added
Dissolving, is warming up to 60 DEG C, and acetic anhydride 112g (0.11mol) is slowly added dropwise, and completion of dropping in half an hour continues to stir 1 hour, subtracted
Pressure steams toluene, obtains five acetyl ursin solids.10% aqueous ammonium chloride solution 80g is directly added into flask again
(0.15mol), is warming up to 70 DEG C, stirring reaction 2 hours, is cooled to room temperature, separates out crystallization, filtering and drying to obtain to ursin
24.5g, yield 90%.
Embodiment 2
Four acetyl ursin 88g (0.2mol) are put into the three-necked flask with stirring, 300ml chloroforms, stirring is added
Dissolving, is warming up to 60 DEG C, and chloroacetic chloride 23.5g (0.3mol) is slowly added dropwise, and completion of dropping in 1 hour continues to stir 2 hours, subtracted
Pressure steams chloroform, obtains five acetyl ursin solids.10% aqueous ammonium chloride solution 321g is directly added into flask again
(0.6mol), is warming up to 70 DEG C, stirring reaction 2 hours, is cooled to room temperature, separates out crystallization, filtering and drying to obtain to ursin
45.2g, yield 83%.
Embodiment 3：
Four acetyl ursin 2.2kg (5mol) are put into 20 liters of three-necked flasks with stirring, the chloroethenes of 5kg bis- are added
Alkane, stirring and dissolving is warming up to 60 DEG C, and acetic anhydride 663g (6.5mol) is slowly added dropwise, and completion of dropping in 1.5 hours continues to stir 1
Hour, decompression steams dichloroethanes, obtains five acetyl ursin solids.10% aqueous ammonium chloride solution is directly added into flask again
5.35kg (10mol), is warming up to 70 DEG C, stirring reaction 3 hours, is cooled to room temperature, separates out crystallization, filtering and drying to obtain to black bearberry
Glycosides 1.2kg, yield 88%.
Above-described is only presently preferred embodiments of the present invention, all timess done in the range of the spirit and principles in the present invention
What modifications, equivalent substitutions and improvements etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of synthetic method of β-ursin, it is characterised in that described ursin by by four acetyl ursin acetylations,
Its product deacetylation is obtained again；
Wherein, four described acetyl ursin by by five acetyl glucose and hydroquinones and its derivative under ionic liquid
Reaction gained.
2. a kind of synthetic method of β-ursin according to claim 1, it is characterised in that four described acetyl ursin
Molar ratio with acetylizing agent, deacetylated base is 1:1-2:2-10.
3. a kind of synthetic method of β-ursin according to claim 1, it is characterised in that four described acetyl ursin
Molar ratio with acetylizing agent, deacetylated base is 1:1.1:1.5.
4. a kind of synthetic method of β-ursin according to claim 1, it is characterised in that described five acetyl glucose
Molar ratio with benzenediol and its derivative is 1:1-2.
5. a kind of synthetic method of β-ursin according to claim 1, it is characterised in that described five acetyl glucose
Molar ratio with benzenediol and its derivative is 1:1.5.
6. the synthetic method of a kind of β-ursin according to claim 1, it is characterised in that described ionic liquid is three
One or both of iron chloride, chlorinated butyl methylimidazole are combined.
7. a kind of synthetic method of β-ursin according to claim 1, it is characterised in that the second used in the acetylation
Acylating agent is the one or more in chloroacetic chloride, acetic anhydride and glacial acetic acid.
8. a kind of synthetic method of β-ursin according to claim 1, it is characterised in that the reaction temperature of the acetylation
Spend for 50-100 DEG C, the reaction time is 1-3 hours.
9. the synthetic method of a kind of β-ursin according to claim 1, it is characterised in that used in described deacetylation
Reagent be aqueous ammonium chloride solution.
10. the synthetic method of a kind of β-ursin according to claim 1, it is characterised in that described deacetylation
Reaction temperature is 60-80 DEG C, and the reaction time is 1-3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710605643.2A CN107216359A (en) | 2017-07-24 | 2017-07-24 | A kind of synthetic method of β ursin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710605643.2A CN107216359A (en) | 2017-07-24 | 2017-07-24 | A kind of synthetic method of β ursin |
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| CN107216359A true CN107216359A (en) | 2017-09-29 |
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| CN201710605643.2A Pending CN107216359A (en) | 2017-07-24 | 2017-07-24 | A kind of synthetic method of β ursin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343138A (en) * | 2018-04-08 | 2019-10-18 | 和德化学(苏州)有限公司 | Method using solid super-strong acid as catalyst synthesis arbutin |
| CN112358514A (en) * | 2020-10-19 | 2021-02-12 | 浙江拓普药业股份有限公司 | Synthesis process of arbutin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040636A (en) * | 2010-12-28 | 2011-05-04 | 北京贝丽莱斯生物化学有限公司 | Method for synthesizing beta-arbutin by adopting alpha-D-glucose pentaacetate |
| CN103159805A (en) * | 2011-12-14 | 2013-06-19 | 南京华狮化工有限公司 | Method for synthesis of alpha-arbutin |
| CN103524575A (en) * | 2013-05-24 | 2014-01-22 | 湖北阿泰克糖化学有限公司 | Improved beta-arbutin preparation method |
| CN103923133A (en) * | 2014-01-17 | 2014-07-16 | 中国科学院昆明植物研究所 | Method for preparing alpha-arbutin |
| CN105968149A (en) * | 2016-05-06 | 2016-09-28 | 江西金顿香料有限公司 | Preparation method of beta-arbutin |
-
2017
- 2017-07-24 CN CN201710605643.2A patent/CN107216359A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040636A (en) * | 2010-12-28 | 2011-05-04 | 北京贝丽莱斯生物化学有限公司 | Method for synthesizing beta-arbutin by adopting alpha-D-glucose pentaacetate |
| CN103159805A (en) * | 2011-12-14 | 2013-06-19 | 南京华狮化工有限公司 | Method for synthesis of alpha-arbutin |
| CN103524575A (en) * | 2013-05-24 | 2014-01-22 | 湖北阿泰克糖化学有限公司 | Improved beta-arbutin preparation method |
| CN103923133A (en) * | 2014-01-17 | 2014-07-16 | 中国科学院昆明植物研究所 | Method for preparing alpha-arbutin |
| CN105968149A (en) * | 2016-05-06 | 2016-09-28 | 江西金顿香料有限公司 | Preparation method of beta-arbutin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343138A (en) * | 2018-04-08 | 2019-10-18 | 和德化学(苏州)有限公司 | Method using solid super-strong acid as catalyst synthesis arbutin |
| CN112358514A (en) * | 2020-10-19 | 2021-02-12 | 浙江拓普药业股份有限公司 | Synthesis process of arbutin |
| CN112358514B (en) * | 2020-10-19 | 2023-01-31 | 浙江拓普药业股份有限公司 | Synthesis process of arbutin |
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Application publication date: 20170929 |