CN106977439A - A kind of isomerization method of lutein - Google Patents
A kind of isomerization method of lutein Download PDFInfo
- Publication number
- CN106977439A CN106977439A CN201710178784.0A CN201710178784A CN106977439A CN 106977439 A CN106977439 A CN 106977439A CN 201710178784 A CN201710178784 A CN 201710178784A CN 106977439 A CN106977439 A CN 106977439A
- Authority
- CN
- China
- Prior art keywords
- acid
- lutein
- isomerization method
- zeaxanthin
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a kind of isomerization method of lutein, comprise the following steps：Lutein is scattered in a solvent, acid or/and ionic liquid are added, metal salt catalyst is added, catalytic reaction is carried out, obtains zeaxanthin.The isomerization method of the present invention can obtain high content zeaxanthin, high conversion rate, product purity is high, and crude product Lutein content can be down to less than 8%, zeaxanthin is converted into zeaxanthin up to more than 80%, for lutein and provides a kind of economically viable process route.
Description
Technical field
The present invention relates to a kind of isomerization method of lutein.
Background technology
Lutein is a member in carotenoid family, is widely present in the natural plants such as marigold, banana and corn and works as
In.In nature, lutein and zeaxanthin typically exist jointly, and they are widely used in the yolk of poultry, skin and subcutaneous
Skin and the meat coloring of fat coloring, fish and shellfish, used also as food additives.Research shows, maize
Confrontation yellow deposition is more sensitive, and more preferably, application prospect is more preferable, but the content of zeaxanthin will be much in natural plants for coloring effect
Less than lutein.
It is well known that isomerization reaction occurs under strong base catalyst for lutein can generate zeaxanthin.PCT Publication
Described in WO96/02594 and lutein isomer is melted into zeaxanthin in strong alkali solution under conditions of a kind of temperature-control pressure-control
Method, inorganic base used is alkali metal hydroxide, calcium hydroxide, sodium carbonate or ammonium hydroxide, and organic base is ethamine, second
Hydramine or morpholine, only with water as solvent, the conversion ratio of this method Lutein is very low, and only only 10%~20%.
Therefore, it is necessary to develop a kind of new lutein isomer method.
The content of the invention
It is an object of the invention to provide a kind of isomerization method of lutein.
The technical solution used in the present invention is：
A kind of isomerization method of lutein, comprises the following steps：Lutein is scattered in a solvent, add acid or/and ion
Liquid, adds metal salt catalyst, carries out catalytic reaction, obtains zeaxanthin.
Described solvent is n-hexane, dichloromethane, hexamethylene, petroleum ether, ethyl acetate, acetone, benzene, toluene, diformazan
At least one of benzene, methanol, ethanol, water.
Described lutein, the mass volume ratio of solvent are 1g：（10~30）mL.
Described acid is at least one of organic acid, inorganic acid, and addition is the 0.1%~5% of lutein quality.
Described organic acid is in formic acid, acetic acid, propionic acid, ethanedioic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, benzene sulfonic acid
At least one, described inorganic acid is at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, perchloric acid, hydrobromic acid, hydroiodic acid.
Described ionic liquid is pyrrole hydrochloride, trimethylamine hydrochloride, triethylamine hydrochloride, tetrabutyl phosphonium bromide phosphorus, three
At least one of butyl ethyl phosphonium bromide, N- hexyl pyridines hexafluorophosphate, N- hexyl pyridinium tetrafluoroborate salt, addition is
The 0.1%~5% of lutein quality.
Described metal salt catalyst is at least one of Cu-series catalyst, Fe-series catalyst, and addition is lutein
The 0.05%~1% of quality.
Described Cu-series catalyst is acetylacetone copper, copper sulphate, copper acetate, cuprous iodide, stannous chloride, cuprous bromide
At least one of.
Described Fe-series catalyst is at least one of iron chloride, ferric acetyl acetonade, carbonyl iron, ferric sulfate.
Described catalytic reaction is carried out at 30 DEG C~80 DEG C, and the reaction time is 5~12 hours.
The beneficial effects of the invention are as follows：The isomerization method of the present invention can obtain high content zeaxanthin, high conversion rate,
Product purity is high, and the crude product Lutein content prepared can be down to less than 8%, zeaxanthin up to more than 80%,
Zeaxanthin, which is converted into, for lutein provides a kind of economically viable process route.
Embodiment
A kind of isomerization method of lutein, comprises the following steps：Lutein is scattered in a solvent, add acid or/and
Ionic liquid, adds metal salt catalyst, carries out catalytic reaction, obtains zeaxanthin.
It is preferred that, described solvent is n-hexane, dichloromethane, hexamethylene, petroleum ether, ethyl acetate, acetone, benzene, first
At least one of benzene, dimethylbenzene, methanol, ethanol, water.
It is preferred that, described lutein, the mass volume ratio of solvent are 1g：（10~30）mL.
It is preferred that, described acid is at least one of organic acid, inorganic acid, addition for lutein quality 0.1%~
5%。
It is preferred that, described organic acid is formic acid, acetic acid, propionic acid, ethanedioic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, benzene sulphur
At least one of acid, described inorganic acid be in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, perchloric acid, hydrobromic acid, hydroiodic acid at least
It is a kind of.
It is preferred that, described ionic liquid is pyrrole hydrochloride, trimethylamine hydrochloride, triethylamine hydrochloride, tetrabutyl bromine
Change at least one of phosphorus, tributyl ethyl phosphonium bromide phosphorus, N- hexyl pyridines hexafluorophosphate, N- hexyl pyridinium tetrafluoroborate salt,
Addition is the 0.1%~5% of lutein quality.
It is preferred that, described metal salt catalyst is at least one of Cu-series catalyst, Fe-series catalyst, and addition is
The 0.05%~1% of lutein quality.
It is preferred that, described Cu-series catalyst is acetylacetone copper, copper sulphate, copper acetate, cuprous iodide, stannous chloride,
At least one of cuprous bromide.
It is preferred that, described Fe-series catalyst is at least one of iron chloride, ferric acetyl acetonade, carbonyl iron, ferric sulfate.
It is preferred that, described catalytic reaction is carried out at 30 DEG C~80 DEG C, and the reaction time is 5~12 hours.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
10g lutein is dissolved in 200mL petroleum ethers, 0.01g pyrrole hydrochlorides is added, adds 0.005g acetylacetone coppers, is risen
Temperature is to 60 DEG C, and stirring reaction 8 hours obtains high content zeaxanthin.
After tested, the high content zeaxanthin product Lutein content is 7.2%, and zeaxanthin is 88.3%.
Embodiment 2：
10g lutein is dissolved in the mixed solution that 200mL n-hexanes and 100mL water are constituted, 0.1g acetic acid is added, adds
0.05g stannous chlorides, are warming up to 68 DEG C, stirring reaction 10 hours obtains high content zeaxanthin.
After tested, the high content zeaxanthin product Lutein content is 12%, and zeaxanthin is 84.5%.
Embodiment 3：
10g lutein is dissolved in 150mL dichloromethane, 0.5g propionic acid is added, adds 0.1g copper sulphate, be warming up to 30 DEG C, stir
Reaction 12 hours is mixed, high content zeaxanthin is obtained.
After tested, the high content zeaxanthin product Lutein content is 19.4%, and zeaxanthin is 78%.
Embodiment 4：
10g lutein is dissolved in 100mL petroleum ethers, 0.2g phosphoric acid is added, adds 0.05g ferric acetyl acetonades, be warming up to 80 DEG C,
Stirring reaction 12 hours, obtains high content zeaxanthin.
After tested, the high content zeaxanthin product Lutein content is 20%, and zeaxanthin is 76.5%.
Embodiment 5：
10g lutein is dissolved in 100mL petroleum ethers, 0.1g triethylamine hydrochlorides is added, adds 0.05g ferric acetyl acetonades, is risen
Temperature is to 78 DEG C, and stirring reaction 5 hours obtains high content zeaxanthin.
After tested, the high content zeaxanthin product Lutein content is 7.8%, and zeaxanthin is 89.5%.
Note：Lutein in embodiment 1~5 is the method purifying that commercially available lutein is provided according to patent US5780693
, wherein lutein content is 93%, and zeaxanthin is 6.1%.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of isomerization method of lutein, it is characterised in that：Comprise the following steps：Lutein is scattered in a solvent, plus
Enter acid or/and ionic liquid, add metal salt catalyst, carry out catalytic reaction, obtain zeaxanthin.
2. isomerization method according to claim 1, it is characterised in that：Described solvent is n-hexane, dichloromethane, ring
At least one of hexane, petroleum ether, ethyl acetate, acetone, benzene,toluene,xylene, methanol, ethanol, water.
3. isomerization method according to claim 1, it is characterised in that：Described lutein, the mass volume ratio of solvent
For 1g：（10~30）mL.
4. isomerization method according to claim 1, it is characterised in that：Described acid be organic acid, inorganic acid in extremely
Few one kind, addition is the 0.1%~5% of lutein quality.
5. isomerization method according to claim 4, it is characterised in that：Described organic acid be formic acid, acetic acid, propionic acid,
At least one of ethanedioic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, benzene sulfonic acid, described inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid,
At least one of nitric acid, perchloric acid, hydrobromic acid, hydroiodic acid.
6. isomerization method according to claim 1, it is characterised in that：Described ionic liquid is pyrrole hydrochloride, three
Methylamine hydrochloride, triethylamine hydrochloride, tetrabutyl phosphonium bromide phosphorus, tributyl ethyl phosphonium bromide phosphorus, N- hexyl pyridines hexafluorophosphate, N-
At least one of hexyl pyridinium tetrafluoroborate salt, addition is the 0.1%~5% of lutein quality.
7. isomerization method according to claim 1, it is characterised in that：Described metal salt catalyst is catalyzed for copper system
At least one of agent, Fe-series catalyst, addition are the 0.05%~1% of lutein quality.
8. isomerization method according to claim 7, it is characterised in that：Described Cu-series catalyst be acetylacetone copper,
At least one of copper sulphate, copper acetate, cuprous iodide, stannous chloride, cuprous bromide.
9. isomerization method according to claim 7, it is characterised in that：Described Fe-series catalyst is iron chloride, acetyl
At least one of acetone iron, carbonyl iron, ferric sulfate.
10. isomerization method according to claim 1, it is characterised in that：Described catalytic reaction is at 30 DEG C~80 DEG C
Carry out, the reaction time is 5~12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710178784.0A CN106977439B (en) | 2017-03-23 | 2017-03-23 | A kind of isomerization method of lutein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710178784.0A CN106977439B (en) | 2017-03-23 | 2017-03-23 | A kind of isomerization method of lutein |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106977439A true CN106977439A (en) | 2017-07-25 |
| CN106977439B CN106977439B (en) | 2018-10-02 |
Family
ID=59339018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710178784.0A Active CN106977439B (en) | 2017-03-23 | 2017-03-23 | A kind of isomerization method of lutein |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106977439B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586306A (en) * | 2018-05-23 | 2018-09-28 | 华东理工大学 | A method of lutein and zeaxanthin are detached using ionic liquid strengthening extraction |
| CN110143904A (en) * | 2019-06-26 | 2019-08-20 | 班磊 | A kind of preparation method of semi-synthetic astaxanthin intermediate zeaxanthin |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178787A (en) * | 1996-10-04 | 1998-04-15 | 霍夫曼-拉罗奇有限公司 | Converting method for lutein |
| US6376722B1 (en) * | 1997-10-31 | 2002-04-23 | Vicente Ernesto Ridaura Sanz | Lutein to zeaxanthin isomerization process and product |
| US20050119506A1 (en) * | 2002-02-06 | 2005-06-02 | University Of Maryland, College Park | Method for production of beta-cryptoxanthin and alpha-cryptoxanthin from commerically available lutein |
| CN100338162C (en) * | 2002-03-26 | 2007-09-19 | Dsm知识产权资产公司 | Esterification of xanthophylls |
| WO2007136428A2 (en) * | 2006-01-19 | 2007-11-29 | Solazyme, Inc. | Nutraceutical compositions from microalgae and related methods of production and administration |
| CN101182302A (en) * | 2007-12-14 | 2008-05-21 | 大连医诺生物有限公司 | Method for preparing compositions containing zeaxanthin |
| CN104447469A (en) * | 2014-12-08 | 2015-03-25 | 晨光生物科技集团股份有限公司 | Method for effectively preparing zeaxanthin from marigold oleoresin |
-
2017
- 2017-03-23 CN CN201710178784.0A patent/CN106977439B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178787A (en) * | 1996-10-04 | 1998-04-15 | 霍夫曼-拉罗奇有限公司 | Converting method for lutein |
| US6376722B1 (en) * | 1997-10-31 | 2002-04-23 | Vicente Ernesto Ridaura Sanz | Lutein to zeaxanthin isomerization process and product |
| US20050119506A1 (en) * | 2002-02-06 | 2005-06-02 | University Of Maryland, College Park | Method for production of beta-cryptoxanthin and alpha-cryptoxanthin from commerically available lutein |
| CN100338162C (en) * | 2002-03-26 | 2007-09-19 | Dsm知识产权资产公司 | Esterification of xanthophylls |
| WO2007136428A2 (en) * | 2006-01-19 | 2007-11-29 | Solazyme, Inc. | Nutraceutical compositions from microalgae and related methods of production and administration |
| CN101182302A (en) * | 2007-12-14 | 2008-05-21 | 大连医诺生物有限公司 | Method for preparing compositions containing zeaxanthin |
| CN104447469A (en) * | 2014-12-08 | 2015-03-25 | 晨光生物科技集团股份有限公司 | Method for effectively preparing zeaxanthin from marigold oleoresin |
Non-Patent Citations (3)
| Title |
|---|
| FREDERICK KHACHIK: "An Efficient Conversion of (3R,3"R,6"R)-Lutein to (3R,3"S,6"R)-Lutein (3"-Epilutein) and (3R,3"R)-Zeaxanthin", 《JOURNAL OF NATURAL PRODUCTS》 * |
| 谢晓菲 等: "关于叶黄素的异构化反应的研究", 《科学时代》 * |
| 陈佳 等: "由天然叶黄素转化为玉米黄素的工艺参数的研究", 《天然产物研究与开发》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586306A (en) * | 2018-05-23 | 2018-09-28 | 华东理工大学 | A method of lutein and zeaxanthin are detached using ionic liquid strengthening extraction |
| CN110143904A (en) * | 2019-06-26 | 2019-08-20 | 班磊 | A kind of preparation method of semi-synthetic astaxanthin intermediate zeaxanthin |
| CN110143904B (en) * | 2019-06-26 | 2021-07-27 | 班磊 | Preparation method of zeaxanthin as intermediate of semi-synthetic astaxanthin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106977439B (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106977439B (en) | A kind of isomerization method of lutein | |
| CN104945208A (en) | Method for preparing allyl alcohol compounds from alpha,beta-unsaturated aldehyde ketones | |
| CN104841421A (en) | Catalyst composition and preparation method thereof, and method for preparing o-phenylphenol by using catalyst composition | |
| CN100594205C (en) | Method for synthesizing 2,7-dimethyl-octa-2,4,6-trienedial | |
| CN107778204B (en) | Preparation method of feloxicib intermediate | |
| CN106518631B (en) | A kind of preparation method of veratrole | |
| CN102153434B (en) | Method for preparing aryl ketone | |
| CN103665063B (en) | A kind of method preparing isopropyl-β-D-thiogalactoside(IPTG) | |
| CN103709209A (en) | Isopropyl-beta-D-thiogalactoside preparation method | |
| CN105152850A (en) | Method for synthesizing cis/trans-3,3,3-trifluoro-1-chloropropylene | |
| CN104492484B (en) | Olefin isomerization catalyst and application thereof | |
| KR101302777B1 (en) | Preparation of 4-ketolutein and use as a food additive | |
| CN103951546B (en) | Novel synthetic process of thymol | |
| CN102267918B (en) | Method for preparing betaine hydrochloride | |
| CN103588633B (en) | The preparation technology of 5 (6)-decylenic acids | |
| CN103041834B (en) | Catalyst for preparing isoamylene by splitting decomposition of t-amyl-methyl ether and preparation method and application thereof | |
| CN102351633B (en) | Preparation method of p-cymene | |
| CN104072360A (en) | Synthetic method for natural cinnamic acid | |
| CN102153462A (en) | Method for synthesizing tanshinol | |
| CN101307016B (en) | Method for synthesizing 2,6-diisopropyl-4-phenoxy phenylthiourea | |
| CN103694286B (en) | Prepare the method for isopropyl-β-D-thiogalactoside(IPTG) | |
| CN103694285B (en) | A kind of preparation method of isopropyl-β-D-thiogalactoside(IPTG) | |
| CN109647508B (en) | Catalyst for synthesizing p-methyl benzaldehyde | |
| CN103694284B (en) | A kind of preparation technology of isopropyl-β-D-thiogalactoside(IPTG) | |
| CN101148434B (en) | Method for synthesizing pentadecane triphenyl phosphonium salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Isomerization method of xanthophyll Effective date of registration: 20200107 Granted publication date: 20181002 Pledgee: Bank of China, Limited by Share Ltd, Guangzhou, Panyu branch Pledgor: Guangzhou Wisdom Bio-Technology Co., Ltd. Registration number: Y2020440000002 |
|
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 510555 No.78 Fenghuang SANHENG Road, Zhongxin Guangzhou Knowledge City, Huangpu District, Guangzhou, Guangdong Province Patentee after: GUANGZHOU WISDOM BIO-TECHNOLOGY Co.,Ltd. Address before: 510530, 17, Fenghuang three road, Guangzhou, Guangzhou, Guangdong, China, five rooms 450 Patentee before: GUANGZHOU WISDOM BIO-TECHNOLOGY Co.,Ltd. |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20210310 Granted publication date: 20181002 Pledgee: Bank of China Limited by Share Ltd. Guangzhou Panyu branch Pledgor: GUANGZHOU WISDOM BIO-TECHNOLOGY Co.,Ltd. Registration number: Y2020440000002 |