CN106977439B - A kind of isomerization method of lutein - Google Patents
A kind of isomerization method of lutein Download PDFInfo
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- CN106977439B CN106977439B CN201710178784.0A CN201710178784A CN106977439B CN 106977439 B CN106977439 B CN 106977439B CN 201710178784 A CN201710178784 A CN 201710178784A CN 106977439 B CN106977439 B CN 106977439B
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- acid
- lutein
- zeaxanthin
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- 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
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- 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
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- 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
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Abstract
The invention discloses a kind of isomerization methods of lutein, include the following steps：In a solvent by lutein dispersion, acid or/and ionic liquid is added, adds metal salt catalyst, carries out catalysis reaction, obtain 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 8% or less, zeaxanthin is converted into zeaxanthin up to 80% or more, for lutein and provides a kind of economically viable process route.
Description
Technical field
The present invention relates to a kind of isomerization methods 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 generally exist jointly, 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.Studies have shown that maize
Confrontation yellow deposition is more sensitive, and more preferably, application prospect is more preferable for coloring effect, but the content of zeaxanthin will be much in natural plants
Less than lutein.
It is well known that isomerization reaction occurs under strong base catalyst for lutein can generate zeaxanthin.PCT Publication
It is 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 be alkali metal hydroxide, calcium hydroxide, sodium carbonate or ammonium hydroxide, organic base be ethamine, second
Hydramine or morpholine only use water as solvent, and 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.
Invention content
The purpose of the present invention is to provide a kind of isomerization methods of lutein.
The technical solution used in the present invention is：
A kind of isomerization method of lutein, includes the following steps：By lutein dispersion in a solvent, be added acid or/and
Ionic liquid adds metal salt catalyst, carries out catalysis reaction, obtains zeaxanthin.
The solvent is n-hexane, dichloromethane, hexamethylene, petroleum ether, ethyl acetate, acetone, benzene, toluene, diformazan
At least one of benzene, methanol, ethyl alcohol, water.
The mass volume ratio of the lutein, solvent is 1g：（10~30）mL.
The acid is at least one of organic acid, inorganic acid, and additive amount is the 0.1%~5% of lutein quality.
The organic acid is in formic acid, acetic acid, propionic acid, ethanedioic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, benzene sulfonic acid
At least one, the inorganic acid are at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, perchloric acid, hydrobromic acid, hydroiodic acid.
The 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, additive amount is
The 0.1%~5% of lutein quality.
The metal salt catalyst is at least one of Cu-series catalyst, Fe-series catalyst, and additive amount is lutein
The 0.05%~1% of quality.
The Cu-series catalyst is acetylacetone copper, copper sulphate, copper acetate, cuprous iodide, stannous chloride, cuprous bromide
At least one of.
The Fe-series catalyst is at least one of iron chloride, ferric acetyl acetonade, carbonyl iron, ferric sulfate.
The catalysis reaction carries 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, the crude product Lutein content being prepared can be down to 8% hereinafter, zeaxanthin up to 80% or more,
It is converted into zeaxanthin for lutein and provides a kind of economically viable process route.
Specific implementation mode
A kind of isomerization method of lutein, includes the following steps：By lutein dispersion in a solvent, be added acid or/and
Ionic liquid adds metal salt catalyst, carries out catalysis reaction, obtains zeaxanthin.
Preferably, the solvent is n-hexane, dichloromethane, hexamethylene, petroleum ether, ethyl acetate, acetone, benzene, first
At least one of benzene, dimethylbenzene, methanol, ethyl alcohol, water.
Preferably, the lutein, solvent mass volume ratio be 1g：（10~30）mL.
Preferably, the acid is organic acid, at least one of inorganic acid, additive amount be lutein quality 0.1%~
5%。
Preferably, the organic acid is formic acid, acetic acid, propionic acid, ethanedioic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, benzene sulphur
At least one of acid, the inorganic acid be sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, perchloric acid, hydrobromic acid, in hydroiodic acid at least
It is a kind of.
Preferably, the 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,
Additive amount is the 0.1%~5% of lutein quality.
Preferably, the metal salt catalyst is at least one of Cu-series catalyst, Fe-series catalyst, and additive amount is
The 0.05%~1% of lutein quality.
Preferably, the Cu-series catalyst be acetylacetone copper, copper sulphate, copper acetate, cuprous iodide, stannous chloride,
At least one of cuprous bromide.
Preferably, the Fe-series catalyst is at least one of iron chloride, ferric acetyl acetonade, carbonyl iron, ferric sulfate.
Preferably, catalysis reaction carries 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 are added, add 0.005g acetylacetone,2,4-pentanediones
Copper is warming up to 60 DEG C, is stirred to react 8 hours, obtains high-content zeaxanthin.
After tested, which is 7.2%, zeaxanthin 88.3%.
Embodiment 2：
10g lutein is dissolved in the mixed solution that 200mL n-hexanes and 100mL water are formed, 0.1g acetic acid is added, then add
Enter 0.05g stannous chlorides, be warming up to 68 DEG C, is stirred to react 10 hours, obtains high-content zeaxanthin.
After tested, which is 12%, zeaxanthin 84.5%.
Embodiment 3：
10g lutein is dissolved in 150mL dichloromethane, 0.5g propionic acid is added, adds 0.1g copper sulphate, is warming up to 30
DEG C, it is stirred to react 12 hours, obtains high-content zeaxanthin.
After tested, which is 19.4%, zeaxanthin 78%.
Embodiment 4：
10g lutein is dissolved in 100mL petroleum ethers, 0.2g phosphoric acid is added, adds 0.05g ferric acetyl acetonades, is warming up to
It 80 DEG C, is stirred to react 12 hours, obtains high-content zeaxanthin.
After tested, which is 20%, zeaxanthin 76.5%.
Embodiment 5：
10g lutein is dissolved in 100mL petroleum ethers, 0.1g triethylamine hydrochlorides are added, add 0.05g acetylacetone,2,4-pentanediones
Iron is warming up to 78 DEG C, is stirred to react 5 hours, obtains high-content zeaxanthin.
After tested, which is 7.8%, zeaxanthin 89.5%.
Note：Lutein in Examples 1 to 5 is that commercially available lutein is purified according to the method that patent US5780693 is provided
, wherein lutein content is 93%, zeaxanthin 6.1%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (4)
1. a kind of isomerization method of lutein, it is characterised in that：Include the following steps：In a solvent by lutein dispersion, add
Enter acid or/and ionic liquid, adds metal salt catalyst, carry out catalysis reaction, obtain zeaxanthin；The acid is organic
At least one of acid, inorganic acid, additive amount are the 0.1%~5% of lutein quality；The organic acid be formic acid, acetic acid,
At least one of propionic acid, ethanedioic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, benzene sulfonic acid, the inorganic acid be sulfuric acid, hydrochloric acid,
At least one of phosphoric acid, nitric acid, perchloric acid, hydrobromic acid, hydroiodic acid；The ionic liquid is pyrrole hydrochloride, trimethylamine
Hydrochloride, triethylamine hydrochloride, tetrabutyl phosphonium bromide phosphorus, tributyl ethyl phosphonium bromide phosphorus, N- hexyl pyridines hexafluorophosphate, N- hexyls
At least one of pyridinium tetrafluoroborate salt, additive amount are the 0.1%~5% of lutein quality；The metal salt catalyst
For at least one of Cu-series catalyst, Fe-series catalyst, additive amount is the 0.05%~1% of lutein quality；The copper
Series catalysts are at least one of acetylacetone copper, copper sulphate, copper acetate, cuprous iodide, stannous chloride, cuprous bromide；Institute
The Fe-series catalyst stated is at least one of iron chloride, ferric acetyl acetonade, carbonyl iron, ferric sulfate.
2. isomerization method according to claim 1, it is characterised in that：The solvent is n-hexane, dichloromethane, ring
At least one of hexane, petroleum ether, ethyl acetate, acetone, benzene,toluene,xylene, methanol, ethyl alcohol, water.
3. isomerization method according to claim 1, it is characterised in that：The mass volume ratio of the lutein, solvent
For 1g：(10~30) mL.
4. isomerization method according to claim 1, it is characterised in that：The catalysis react at 30 DEG C~80 DEG C into
Row, reaction time are 5~12 hours.
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| CN108586306B (en) * | 2018-05-23 | 2020-01-10 | 华东理工大学 | Method for separating lutein and zeaxanthin by adopting ionic liquid enhanced extraction |
| CN110143904B (en) * | 2019-06-26 | 2021-07-27 | 班磊 | Preparation method of zeaxanthin as intermediate of semi-synthetic astaxanthin |
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| CN1082507C (en) * | 1996-10-04 | 2002-04-10 | 霍夫曼-拉罗奇有限公司 | Converting method for lutein |
| IN189750B (en) * | 1997-10-31 | 2003-04-19 | Bioquimex Reka S A De C V | |
| AU2003217324B2 (en) * | 2002-02-06 | 2008-07-03 | University Of Maryland, College Park | Method for production of beta-cryptoxanthin and alpha-cryptoxanthin from commercially available lutein |
| MXPA04009248A (en) * | 2002-03-26 | 2005-01-25 | Prodemex Sa De Cv | Esterification of xanthophylls. |
| ES2682455T3 (en) * | 2006-01-19 | 2018-09-20 | Terravia Holdings, Inc. | Compositions derived from microalgae to improve the health and appearance of the skin |
| CN101182302B (en) * | 2007-12-14 | 2010-08-18 | 大连医诺生物有限公司 | Method for preparing compositions containing zeaxanthin |
| CN104447469B (en) * | 2014-12-08 | 2016-08-17 | 晨光生物科技集团股份有限公司 | Lutein extract efficiently prepares the method for cryptoxanthin |
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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 |
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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. |
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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 |
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